Packaging unit

ABSTRACT

A packaging unit has a container ( 1 ) for holding a product, a closure ( 2 ) and an opening or closure cylinder ( 14 ) for dispensing product from the container ( 1 ). The closure ( 2 ) closes the opening ( 14 ). The packaging unit has at least one receiving means ( 3 ), for a plurality of additive portions ( 6, 11, 21 ) of in each case less than 50 ml, which may be blister packs. The additive ( 16 ) held in the additive portions ( 6, 11, 21 ) may be one or more aromatic, colorant or surfactant. The receiving means ( 3 ) for additive portions ( 6, 11, 21 ) can be fixed releasably to the packaging unit.

The invention relates to a package consisting of a container forproducts and a device arranged on this container for accommodatingadditive portions.

BACKGROUND OF THE INVENTION

There has long been a requirement to be able to individualize productsfor specific customer requirements or to allow customers toindividualize them to a certain extent. One particularly suitable mediumfor individualizing a product is its packaging, as this forms theimmediate interface between consumer and product.

It is thus desirable to combine means for individualizing or furtherfunctionalizing a product directly with the package for a product.

In particular when perfuming products such as for example cleaningagents, detergents and the like, it is at present still conventional tosell the entire sales unit with one specific fragrance. However, a useroften wants a cleaning product to release a different fragrance fordifferent areas of application. It is, for example, desirable for acleaning agent to emit a more intense fragrance for the toilet area thanin a living area, where intense fragrances often tend to be consideredtroublesome. It has thus hitherto been necessary to use a plurality ofspecial cleaning products having the corresponding fragrances, despitethe preparations with a cleaning action being in each case identical orat least very similar.

Specifically in the case of very aggressive cleaning preparations theproblem furthermore arises that the aggressive cleaning components alsobreak down the fragrances present in the preparations, resulting in onlyshort storage stability.

In addition to the preparation of individually perfumed products, thereis a further requirement for a product package to be designed such thatthe fragrance of the product contained in the package may beolfactometrically perceptible.

Finally, packages are also increasingly being additionallyfunctionalized by providing fragrance-emitting agents on the packagewhich release a specific fragrance into the surroundings of the packageand so additionally assume the function of a room fragrancing product.

Blister packs are conventionally used, for example in relation toproviding pharmaceutical preparations, for ensuring that products areindividually portioned as required. In such cases, individual doses ofpharmaceutical preparations, for example in the form of tablets, are ineach case packaged in one compartment of a blister pack.

Such a blister pack conventionally consists of a first flat element, inwhich a plurality of individual, conventionally well-shaped, separatecavities are formed for accommodating product doses and a second flatelement which is joined to the first flat element over the surfacethereof and closes the cavities.

The first flat element, in which the cavities are made, conventionallyconsists of a piece of plastics film in which the cavities are shaped,for example by thermoforming.

The second flat element which closes the cavities consists of a materialwhich is sufficiently strong to avoid unintentional opening, but whichcan be opened by the application of appropriate pressure, for example bypressing with the thumb or tearing the film/foil with a fingernail.

Exerting pressure on a compartment of the blister pack results inpressure being exerted on the product located in the compartment, theproduct then ultimately puncturing the lower film/foil.

A blister pack may also be embodied such that the second flat elementwhich closes the cavities is made stronger such that the well-shapedcavities of the first flat element are opened by the applied pressureand the second flat element which closes the cavities remains undamaged

DE4239082 discloses the use of such a blister pack forfragrance-emitting substances. The blister pack here consists of aplurality of compartments filled with fragrance, the reverse side of theblister pack being provided with an adhesive layer which can be stuckonto a garment or human skin.

A disadvantageous feature of this solution is that the blister packcannot be non-detachably fastened to a carrier object. The blister packmay accordingly always be completely detached from the carrier object,such as for example human skin. However, in particular for salespackages this is not desirable and is disadvantageous in that a blisterpack can fall off unintentionally, for example due to adhesive failure,from the sales package or, with criminal intent, be removed from thesales container.

Moreover, the product in the well-shaped indentations of the blisterpack cannot be released by the destruction of the lower film/foil,since, according to the teaching of DE4239082, this lower film/foil isadhesively bonded over its entire surface to the carrier object. Thus,when a well-shaped cavity is destroyed to release a product portion, itis not possible to avoid this product coming into contact with theuser's hands. However, for many applications, such as for example whenapportioning cleaning substances or highly concentrated fragrance oils,this is unwanted.

WO2004/084660 discloses arranging fragrance-emitting substances in aclosure flap of a container. Fragrance-emitting substances are herearranged in a chamber of the container closure, said chamber beingsealed with a film/foil which may be removed in order to use the cap ofthe room fragrancer, such that fragrance may be released from theclosure flap into the surroundings. A disadvantageous feature of thissolution is the comparatively large size of the closure which is thusinconvenient for the consumer to handle. Because the internal volume ofthe closure is virtually completely filled with a fragrance, there isvirtually no further dispensing volume available, such that the closurecannot in general be used as a dispensing unit, as is the case forexample for rinse conditioner or floor cleaner closures. Due to itsnecessarily enlarged size in comparison with conventional closures, thestorage space requirements for containers equipped in this way are alsoincreased, which inevitably also results in increased logistics costs.

CA983437 discloses a container for medical applications, in which it isnecessary to take a prescribed dose of a tablet or capsule inconjunction with a liquid. To this end, a container according toCA983437 comprises means for accommodating the individual doses on theouter wall of the container. These are indentations in the outer wall,into which the individual doses may be inserted or placed. The doseslocated in the indentations may then be fastened in the indentationswith an adhesive tape. A dose can then be removed by lifting and peelingaway the adhesive tape, such that a dose is released and may be removedfrom the indentation in the outer wall of the container.

This solution has the disadvantage that producing such a container iscostly and technically complex. Furthermore, large areas are required,which considerably limits space for promotional and/or descriptivelabels. Moreover, the overall esthetic impression of the container isappreciably impaired thereby. Another disadvantage of this solution isthat preparations in paste or gel form cannot be dispensed and removed.

OBJECT OF THE INVENTION

The object of the present invention is accordingly to provide a packagewhich may be produced inexpensively and which makes it possible toprovide individually packaged, portionable additive units on a containerin a simple and easily usable manner.

The object is achieved according to the invention by a packaging unitcomprising a container for accommodating a product, a closure and anopening closable by the closure for discharging the product from thecontainer, wherein the packaging unit comprises at least one receivingmeans for a plurality of additive portions of in each case less than 50ml, the additive comprising at least one substance from the group offragrances, dyes or surfactants and the receiving means for the additiveportions being detachably fastenable to the packaging unit.

For the purposes of the present application, a packaging unit is takento mean the entire assembly of container, container opening and closure.

The receiving means for a plurality of product portions may, forexample, take the form of a tearable package, cushion package, shrinkpackage, see-through package, blister package, bubble package, contourpackage, push-through package, skin package, stretch package, strippackage, vacuum package, combination package, multicomponent package,multipart package, portion package, consolidated package ormultipackage.

In particular, the receiving means may also take the form of asubstantially dimensionally stable body to which individual additiveportions may be fastened.

The additive portions are in each case enclosed at least in part by aflexible or dimensionally stable container in such a way that theadditive disposed in the portion is not released unintentionally. Theadditive portions may be joined detachably or fixedly to the receivingmeans.

The additive portions may be formed, for example, by a substantiallyflexible blister pack, bubble pack or contour pack, which are thenjoined in suitable manner to the receiving means for fastening to thecontainer.

It is also feasible to shape the additive portions as a dimensionallystable container such as for example a closable cup or vial, which maythen preferably be fastened detachably in the packaging unit.

The receiving means for the additive portions may be fastened to thecontainer using detachable connections deemed suitable by a personskilled in the art. In particular, fastening to the container may beeffected frictionally, interlockingly and/or by material bonding forexample by one or more of the connection types from the group comprisingsnap-in connections, hook-and-loop connections, press connections, meltconnections, adhesive connections, welded connections, brazedconnections, screw connections, keyed connections, clamped connectionsor rebound connections.

The contents of the additive portions may consist for example of one ormore identical or different products such as for example fragrances,cleaning substances, dyes, surfactants, fungicides, enzymes, hygroscopicsubstances and the like.

According to one particular embodiment of the invention, it is possiblefor the container for the additive portions to consist at least in partof a material which allows release of a product enclosed in the additiveportions into the surroundings by diffusion. In addition, in this casethe additive portion may be covered by an additional protective filmwhich initially prevents the product from being released into thesurroundings. The protective film may be removed from an additiveportion for example by tearing or rubbing, such that additive productmay then be released into the surroundings.

The invention is particularly suitable for dimensionally stablecontainers such as cups, cans, buckets, barrels, bottles, jerricans,pots, cartons, drums or tubes, but may also be used for flexiblecontainers such as pouches or bags.

Cans may in particular include ironed cans, ring-pull cans, friction topcans, necked-in cans, open-top cans, open-top vent-hole cans,interlocked sideseam cans, drawn cans, piston cans, convolute cans,tear-strip cans, beaded cans, lidded tins or stepped-rim cans.

Barrels may be selected from the group comprising belly barrels, stavedbarrels, tight barrels, oil drums, semi-tight barrels, dry casks,trundle rolling hoop drums, heavy casks, channel drums or rollingchannel drums.

A bottle may for example take the form of an aerosol bottle, see-throughbottle, drinks bottle, in particular a beer bottle, bocksbeutel,codd-neck bottle, German-type bottle, steinie bottle, stubby bottle,Vichy bottle, wide-necked bottle, as well as a meplat bottle, squeezybottle, dropper bottle, packaging bottle such as for instance a perfumebottle.

For the purposes of the present application cartons are in particulartaken to mean folding cartons such as for example erectable cartons,pull-through cartons, folding bottom cartons, folder cartons, foldingcartons with internal liner, two-piece staple-joined cartons, foldingtube and slide cartons, interlocking bottom cartons, folding telescopecartons and tray lid cartons, window cartons, hinge-cover cartons suchas for example coated hinge-cover cartons or knurled hinge-covercartons, and flap-lid cartons, double cover cartons, tube and slidecartons, chip boxes, telescope cartons, carrying cartons or shippingcartons.

The container opening may in particular comprise a push-in flap, collar,in particular external collar, as well as a mouthpiece or orifice orvalve carrier, cork mouthpiece, crown cork mouthpiece, hole mouthpiece,threaded mouthpiece, sprayer mouthpiece, plughole or bunghole.

The closure may comprise a closing means from the group of lids,tear-off lids, roll-off lids, ring-pull lids, hooded lids, frictiontops, tuck-in tops, open-top lids, film/foil lids, flap lids, cam lids,bayonet closure lids, grooved lids, hinged lids, sliding lids, insertionlids, snap lids, clamp lids, screw lids, snap-fit lids, overlap lids,tuck-in tongues, flaps, external flaps, internal flaps, closing flaps,keystones, plugs, bungs, screw bungs, stoppers, capped stoppers, groundglass stoppers, closing caps, tube caps, crown corks, screw caps, valveprotection caps, closing capsules, bottle capsules, tear-off capsules,crimped capsules and spigots.

The closure and/or the opening of the container may optionally comprisedispensing and discharge aids such as for instance an aerosol valve,pourer, spray cap, spray head, atomizer, dispensing device, dispensingcap, dispensing mouthpiece or a dropper.

For the purposes of the present application, an additive is taken tomean a substance or mixture of substances which, by mixing with theproduct present in the container, is suitable for bringing about orinfluencing, in particular improving, producing, emphasizing orattenuating, a property of the product, for accelerating or retarding aprocess which proceeds over time, or for initiating, inhibiting orcatalyzing a reaction. An additive should furthermore also be taken tomean a substance or mixture of substances which is suitable for bringingabout or influencing a property of the container, in particularfragrance and/or active ingredient release, adsorption or absorption onor in the container.

The additive may for example comprise one or more substances from thegroup of fragrances, bleaching agents, cleaning substances, solvents,surfactants, dyes, enzymes, hygroscopic substances, flame retardants,curing agents, levelling agents, wetting agents, dispersants, foamingagents, defoamers, deaerating agents, corrosion protection agents,biocides, water softeners, preservatives, emulsifiers, stabilizers,vitamins, minerals and the like.

Thanks to the spatial separation achievable with the invention betweencertain added active substances (fragrance, enzymes, bleach etc.) andthe actual product and the portionable additive units arrangedimmediately on the container, the product present in the container maybe formulated in a straightforward manner.

The additive portions of the receiving means may contain identical ordifferent products. It would accordingly be conceivable, for example, toarrange substances having different fragrances in the additive portionsin order to permit the container contents or the container itself to bedifferently perfumed. For example, when using a cleaning liquid with aneutral fragrance which is first mixed with water to obtain a wipe-downpreparation, it is possible to apportion a different fragrance from thereceiving means for the additive portions each time a wipe-down solutionis prepared. On the one hand, this prevents olfactometric adaptation toone specific fragrance, while on the other hand a fragrance can beselected depending on the requirements of a specific room in which theproduct is used (toilet, living room, kitchen). It is then no longernecessary to use several specially perfumed cleaning substances for thispurpose, an outcome which is also desirable from an environmental andresource conservation aspect.

Another substantial advantage of the invention is the simple and thusinexpensive manner in which it may be produced. It is accordinglypossible to have the receiving means for the additive portionsmanufactured completely independently from a container. A receivingmeans for the additive portions is subsequently fastened to thecontainer in accordance with the disclosed teaching of the invention.

The receiving means for the additive portions is detachable by theconsumer at any time, whereby according to a preferred embodiment of theinvention the receiving means for the additive portions may also befastened to articles outside the product container.

It is accordingly, for example, also possible, once the additiveportions have been completely consumed, to remove them from thecontainer and to arrange a new unconsumed receiving means for additiveportions on the container.

Polymeric Support Material

According to a preferred embodiment of the invention, the activeadditive substances are bound to or in a polymeric support material.Fragrances are particularly preferably bound in or to a polymericsupport material.

Polymers or polymer blends which are suitable for thefragrance-containing particles are in general any such which meet theabove-stated criteria with regard to melting or softening temperature.Fragrance-releasing systems which are preferred for the purposes of thepresent application are characterized in that the polymeric supportmaterial contains at least one substance from the group comprisingethylene/vinyl acetate copolymers, low or high density polyethylene(LDPE, HDPE) or mixtures thereof, polypropylene,polyethylene/polypropylene copolymers, polyether/polyamide blockcopolymers, styrene/butadiene (block) copolymers, styrene/isoprene(block) copolymers, styrene/ethylene/butylene copolymersacrylonitrile/butadiene/styrene copolymers, acrylonitrile/butadienecopolymers, polyether esters, polyisobutene, polyisoprene,ethylene/ethyl acrylate copolymers, polyamides, polycarbonate,polyesters, polyacrylonitrile, polymethyl methacrylate, polyurethanes,polyvinyl alcohols.

Polyethylene (PE) is a collective term for polyolefin polymerscomprising groupings of the type

CH₂—CH₂

as a characteristic base unit of the polymer chain. Polyethylenes aregenerally produced by polymerizing ethylene by two fundamentallydifferent methods, the high pressure process and the low pressureprocess. Accordingly, the resultant products are frequently respectivelyreferred to as high pressure polyethylenes or low pressurepolyethylenes; they differ mainly with regard to their degree ofbranching and consequently in terms of their degree of crystallinity anddensity. Both processes can be performed as solution polymerization,emulsion polymerization or gas phase polymerization.

The high pressure process yields branched polyethylenes of low density(approx. 0.915-0.935 g/cm³) and degrees of crystallinity of approx.40-50%, which are known as LDPE (low density polyethylene) grades.Products of a higher molar mass and consequently improved strength andstretchability are known by the abbreviation HMW-LDPE (HMW=highmolecular weight). By copolymerizing ethylene with longer-chain olefins,in particular with butene and octene, it is possible to reduce thepronounced degree of branching of the polyethylenes produced by the highpressure process; the copolymers are designated LLD-PE (linear lowdensity polyethylenes).

The macromolecules of polyethylenes produced by the low pressure processare largely linear and unbranched. These polyethylenes, abbreviated HDPE(high density polyethylene), have a degree of crystallinity of 60-80%and a density of approx. 0.94-0.965 g/cm³. They are offered for sale asproducts with high or ultrahigh molar mass (approx. 200,000-5,000,000g/mol or 3,000,000-6,000,000 g/mol) under the abbreviations HD-HMW-PE orUHMW-HD-PE respectively. Medium density products (MDPE) prepared frommixtures of low and high polyethylenes are also commercially obtainable.Linear polyethylenes with densities of <0.918 g/cm³ (VLD-PE=very lowdensity polyethylenes) are only slowly gaining commercial significance.

Polyethylenes have very low water vapor permeability, while thediffusion of gases and aroma substances and essential substances throughpolyethylenes is relatively high. Mechanical characteristics are highlydependent on the molecular size and structure of the polyethylenes. Ingeneral, the degree of crystallinity and density of polyethylenesincrease as the degree of branching falls and the side chains shorten.Shear modulus, hardness, yield point and melting range rise withdensity, while shock resistance, transparency, swellability andsolubility fall. At constant density of the polyethylenes, tensilestrength, elongation, shock resistance, impact strength and creepstrength increase with a rising molar mass. Depending on process controlduring polymerization, it is possible to obtain products havingcharacteristics similar to paraffin wax (M_(r) of around 2000) andproducts having extreme toughness (M_(r) greater than 1 million).

The various grades of polyethylene may be processed by any methodsconventional for thermoplastics.

Polypropylene (PP) is the name for thermoplastic polymers of propyleneof the general formula:

—(CH₂—CH[CH₃])_(n).

The basis for producing polypropylene was Natta's development of thestereospecific polymerization process for propylene in the gas phase orin suspension. This is initiated not only with Ziegler-Natta catalystsbut, increasingly, also by metallocene catalysts and gives rise eitherto highly crystalline isotactic or to less crystalline syndiotactic oramorphous atactic polypropylenes.

Polypropylene is distinguished by elevated hardness, resilience,rigidity and heat resistance. Articles made from polypropylene may evenbriefly be heated to 140° C. At temperatures of below 0° C., a certaindegree of embrittlement of the polypropylene occurs, but this may beshifted to substantially lower temperature ranges by copolymerizingpropylene with ethylene (EPM, EPDM). In general, the impact strength ofpolypropylene may be improved by elastomer modification. In common withall polyolefins, chemical resistance is good. The mechanical propertiesof polypropylenes may be improved by reinforcement with talcum, chalk,wood flour or glass fibers. Polypropylenes are even more susceptible tooxidation and sensitive to light than PE, for which reason it isnecessary to add stabilizers (antioxidants, light stabilizers, UVabsorbers).

Polyether is a term used in macromolecular chemistry to describepolymers whose organic repeat units are joined together by etherfunctions (C—O—C). According to this definition, numerous structurallyvery different polymers belong among polyethers, for examplepolyalkylene glycols (polyethylene glycols, polypropylene glycols andpolyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins,polytetrahydrofurans (polytetramethylene glycols), polyoxetanes,polyphenylene ethers (c.f. polyaryl ethers) or polyetherether ketones(c.f. polyether ketones). Polymers with lateral ether groups, such asinter alia cellulose ethers, starch ethers and vinyl ether polymers, arenot classed among polyethers.

The group of polyethers furthermore also includes functionalizedpolyethers, i.e. compounds with a polyether skeleton which bear stillfurther functional groups, such as for example carboxy, epoxy, allyl oramino groups etc., attached laterally to their main chains. Blockcopolymers of polyethers and polyamides (polyether amides or polyetherblock amides, PEBA) have many uses.

Polyamides (PA) is the name given to polymers whose building blocks arejoined together by amide bonds (—NH—CO—). Naturally occurring polyamidesare peptides, polypeptides and proteins (e.g. protein, wool, silk). Withonly a few exceptions, synthetic polyamides are thermoplastic,chain-like polymers, some of which have gained considerable industrialsignificance as synthetic fibers and materials. Depending on theirchemical structure, “homopolyamides” may be divided into two groups, theaminocarboxylic acid types (AC) and the diaminodicarboxylic acid types(AA-CC; A here denoting amino groups and C carboxy groups). The formerare produced from only one monomer, for example by polycondensation ofan w-aminocarboxylic acid (1) (polyamino acids) or by ring-openingpolymerization of cyclic amides (lactams) (2).

In addition to homopolyamides, some co-polyamides have gainedsignificance. It is conventional to state the composition in qualitativeand quantitative terms, e.g. PA 66/6 (80:20) for polyamides producedfrom 1,6-hexanediamine, adipic acid and ε-caprolactam in a molar ratioof 80:80:20. Due to their particular characteristics, polyamides whichexclusively contain aromatic residues (for example those fromp-phenylenediamine and terephthalic acid) are known generically asaramids or polyaramids (for example Nomex®).

The most frequently used types of polyamides (primarily PA 6 and PA 66)consist of unbranched chains with average molar masses of 15,000 to50,000 g/mol. In a solid state they are partially crystalline and havedegrees of crystallization of 30-60%. Polyamides prepared from buildingblocks with side chains or co-polyamides prepared from very differentcomponents, which are largely amorphous, are an exception. In contrastwith the generally milky-opaque, partially crystalline polyamides, theseare almost crystal clear. The softening temperatures of the commonesthomopolyamides are between 200 and 260° C. (PA 6: 215-220° C., PA 66:255-260° C.).

Polyester is the collective term for polymers whose building blocks arejoined together by ester bonds (—CO—O—). Depending on their chemicalstructure, “homopolyesters” may be divided into two groups,hydroxycarboxylic acid types (AB polyesters) and dihydroxydicarboxylicacid types (AA-BB polyesters). The former are produced from only onemonomer by for example polycondensation of an w-hydroxycarboxylic acid 1or by ring-opening polymerization of cyclic esters (lactones) 2.

Branched and crosslinked polyesters are obtained from thepolycondensation of tri- or polyhydric alcohols with polyfunctionalcarboxylic acids. Polycarbonates (polyesters of carbonic acid) aregenerally also included among polyesters. AB type polyesters (I) areinter alia polyglycolic acid, polylactic acid, polyhydroxybutyric acid[poly(3-hydroxybutyric acid), poly(ε-caprolactone)s andpolyhydroxybenzoic acids.

Purely aliphatic AA-BB type polyesters (II) are polycondensationproducts prepared from aliphatic diols and dicarboxylic acids, which areused inter alia as products with terminal hydroxy groups (as polydiols)for producing polyesterpolyurethanes [for examplepolytetramethyleneadipate]. In quantity terms, AA-BB type polyestersprepared from aliphatic diols and aromatic dicarboxylic acids are of thegreatest industrial significance, in particular polyalkyleneterephthalates, with polyethylene terephthalate (PET), polybutyleneterephthalate (PBT) and poly(1,4-cyclohexanedimethylene terephthalate)s(PCDT) being the most important representatives. The properties of thesetypes of polyesters may be widely varied and adapted to different areasof application by joint use of other aromatic dicarboxylic acids (forexample isophthalic acid) or by using diol mixtures duringpolycondensation.

Purely aromatic polyesters are polyarylates which inter alia includepoly(4-hydroxybenzoic acid). In addition to the previously statedsaturated polyesters, it is also possible to produce unsaturatedpolyesters from unsaturated dicarboxylic acids, which have gainedindustrial significance as polyester resins, in particular asunsaturated polyester resins (UP resins).

Polyesters are generally thermoplastics. Products based on aromaticdicarboxylic acids have pronounced material properties. Purely aromaticpolyarylates are distinguished by elevated thermal stability.

Polyurethanes (PU) is the name given to polymers having macromoleculeswith repeat units linked together by urethane groups —NH—CO—O—.Polyurethanes are generally obtained by polyaddition from dihydric ormore highly hydric alcohols and isocyanates.

Depending on the starting materials selected and their stoichiometricratio, polyurethanes with very different mechanical characteristics areobtained which are used as constituents of adhesives and coatingmaterials (polyurethane resins), as ionomers, as thermoplastic materialfor bearing parts, rollers, tires, rolls and as elastomers of greater orlesser hardness in fiber form (elastomeric fibers, abbreviated to PUEfor these elastane or spandex fibers) or as polyether urethane orpolyester urethane rubber (EU or AU).

Polyurethane foams are obtained on polyaddition if water and/orcarboxylic acids are present since these react with the isocyanates andliberate carbon dioxide which has a blowing and foam-forming action.Flexible polyurethane foams are obtained when using polyalkylene glycolethers as the diols and water as a reaction component, while rigidpolyurethane foams and structural or integral foams are obtained withpolyols and CFC blowing gases (especially R11). Auxiliary materialswhich are additionally required are here for example catalysts,emulsifiers, foam stabilizers (especially polysiloxane/polyethercopolymers), pigments, antioxidants and flame retardants. RIM (reactioninjection molding) was developed in the 1970s to allow the productioneven of complicated shaped articles from polyurethane foam. The RIMprocess is based on rapid apportioning and mixing of the components,injection of the reactive mixture into the mold and rapid curing; thecycle time amounts to only a few minutes. RIM is used to produce, amongother things, automotive body parts, shoe soles, window profiles andtelevision casings.

Polyvinyl alcohols (PVAL, occasionally also PVOH) is the name given topolymers of the general structure

which also contain small proportions (approx. 2%) of structural units ofthe type

Conventional commercial polyvinyl alcohols are offered for sale aswhite-yellowish powders or granules with degrees of polymerization inthe range from approx. 100 to 2500 (molar masses of approx. 4000 to100,000 g/mol). Manufacturers differentiate polyvinyl alcohols bystating the degree of polymerization of the starting polymer, the degreeof hydrolysis, the saponification value or the solution viscosity.

Depending on their degree of hydrolysis, polyvinyl alcohols are solublein water and less strongly polar organic solvents (formamide,dimethylformamide, dimethyl sulfoxide); they are not attacked by(chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcoholsare classed as toxicologically safe and are at least partiallybiodegradable. Water solubility can be reduced by post-treatment withaldehydes (acetalization), by complexation with Ni or Cu salts or bytreatment with dichromates, boric acid or borax. Coatings of polyvinylalcohol are largely impenetrable by gases such as oxygen, nitrogen,helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Polyvinyl alcohols of a specific molecular weight range are preferablyused as materials for the containers, wherein it is preferred accordingto the invention for the water-soluble or water-dispersible container tocomprise a polyvinyl alcohol having a molecular weight in the range from10,000 to 100,000 gmol⁻¹, preferably from 11,000 to 90,000 gmol⁻¹,particularly preferably from 12,000 to 80,000 gmol⁻¹ and in particularfrom 13,000 to 70,000 gmol⁻¹.

In one particularly preferred embodiment of the present invention, thepolymeric support material of the particles consists at least in part ofethylene/vinyl acetate copolymer. The present application accordinglypreferably also provides a fragrance release system, wherein thepolymeric support material contains at least 10 wt. %, preferably atleast 30 wt. %, particularly preferably at least 70 wt. % ofethylene/vinyl acetate copolymer, preferably is completely produced fromethylene/vinyl acetate copolymer.

Ethylene/vinyl acetate copolymer is the name given to copolymers ofethylene and vinyl acetate. This polymer is in principle produced in aprocess comparable to that for the production of low densitypolyethylene (LDPE). As the proportion of vinyl acetate increases, thecrystallinity of the polyethylene is broken down and in this manner themelting and softening points or the hardness of the resultant productsare reduced. The vinyl acetate additionally makes the copolymer morepolar and so improves its adhesion to polar substrates.

The above-described ethylene/vinyl acetate copolymers are commerciallywidely available, for example under the trademark Elvax® (Dupont).Polyvinyl alcohols which are particularly suitable for the purposes ofthe present invention are for example Elvax® 265, Elvax® 240, Elvax® 205W, Elvax® 200 W and Elvax® 360.

Some particularly suitable copolymers and their physical characteristicsmay be found in the table below:

Wt. % vinyl acetate Product name (relative to total weight) Meltingpoint Elvax ® 40 W 40 47° C. Elvax ® 150 33 63° C. Elvax ® 265 28 75° C.Elvax ® 240 28 74° C. Elvax ® 205 W 28 72° C. Elvax ® 200 W 28 71° C.Elvax ® 360 25 78° C. Elvax ® 460 18 88° C. Elvax ® 660 12 96° C.Elvax ® 760 9 100° C. 

For the purposes of the present invention, in particular in the field offragrancing interiors, particularly preferred fragrance release systemsare those in which ethylene/vinyl acetate copolymer is used as thepolymeric support material and this copolymer contains 5 to 50 wt. % ofvinyl acetate, preferably 10 to 40 wt. % of vinyl acetate and inparticular 20 to 30 wt. % of vinyl acetate, in each case relative to thetotal weight of the copolymer.

Fragrance release systems according to the invention contain thepolymeric support materials in the form of particles. Thethree-dimensional shape of these particles is limited only by what istechnically possible during their production. Three-dimensional shapeswhich may thus be considered include any developments which can sensiblybe handled, thus for example cubes, cuboids and correspondingthree-dimensional elements with planar side faces and in particularcylindrical developments with a circular or oval cross-section. Thislatter development encompasses shapes from tablet-shaped particles tocompact cylindrical pieces with a ratio of height to diameter of greaterthan 1. Further possible three-dimensional shapes are spheres,hemispheres or “stretched spheres” in the form of ellipsoidal capsulesas well as regular polyhedrons, for example tetrahedrons, hexahedrons,octahedrons, dodecahedrons, icosahedrons. Star-shaped configurationswith three, four, five, six or more points are furthermore conceivable,as are completely irregular articles, which may for example take theform of a motif. Suitable motifs are selected depending on the area ofapplication of the agents according to the invention, for example animalfigures, such as dogs, horses or birds, floral motifs or representationsof fruit. The motifs may, however, also relate to inanimate articlessuch as vehicles, tools, household items or clothing. Depending on thenature of the selected manufacturing process and/or of a selectedcoating, the surface of the solid particles may comprise irregularities.Due to the numerous possible developments of the particles, the agentsaccording to the invention are not solely distinguished by advantagesduring the production thereof.

Due to the many and varied developments, the fragrance-containingparticles are additionally visually distinguishable for the consumerand, thanks to the purposeful three-dimensional design of theseparticles, they permit a visual differentiation of the agents accordingto the invention which contain fragrances or further active substancesoptionally present in these agents which is particularly advantageouswith regard to product acceptance. The visually perceptible multi-phasenature of these agents may accordingly, for example, emphasize thedifferent modes of action of individual active substances (for examplecleaning function plus additional functions such as glass protection,silver protection etc.).

For the purposes of the present application, particles are taken to meanparticulate materials which, at room temperature, have a solid, i.e.dimensionally stable, non-free-flowing consistency. Preferred particleshave an average diameter of 0.5 to 20 mm, preferably of 1 to 10 mm andin particular of 3 to 6 mm.

The polymeric support materials may be converted into theabove-described particles using any process known to a person skilled inthe art for processing these substances. For the purposes of the presentinvention, extrusion, injection molding and atomization to yield polymerpellets are preferred.

Fragrances

Perfume oils or fragrances which may be used for the purposes of thepresent invention are individual odoriferous compounds, for examplesynthetic products of the ester, ether, aldehyde, ketone, alcohol andhydrocarbon type. Odoriferous compounds of the ester type are forexample benzyl acetate, phenoxyethyl isobutyrate,p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate,ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallylpropionate and benzyl salicylate. Ethers include, for example, benzylethyl ether, aldehydes include, for example, linear alkanals having 8-18C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, ketones include,for example, ionones, α-isomethylionone and methyl cedryl ketone,alcohols include anethole, citronellol, eugenol, geraniol, linalool,phenylethyl alcohol and terpineol, hydrocarbons mainly include terpenessuch as limonene and pinene. Preferably, however, mixtures of variousodoriferous substances which together produce an attractive fragrancenote are used. Such perfume oils may also contain natural odoriferousmixtures, as are obtainable from plant sources, for example pine,citrus, jasmine, patchouli, rose or ylang-ylang oil. Muscatel oil, sageoil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil,lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanumoil and labdanum oil and orange-blossom oil, neroli oil, orange peel oiland sandalwood oil are likewise suitable.

The general description of usable perfumes (see above) here generallyrepresents the various different classes of odoriferous substances. Ifit is to be perceptible, an odoriferous substance must be volatile,wherein, in addition to the nature of the functional groups and thestructure of the chemical compound, an important role is also played bymolar mass. Most odoriferous substances accordingly have molar masses ofup to approx. 200 Dalton, while molar masses of 300 Dalton and abovetend to be an exception. Due to the differing volatility of odoriferoussubstances, the odor of a perfume or fragrance composed of two or moreodoriferous substances varies over the course of vaporization, it beingpossible to subdivide odor impressions into “head or top note”, “heartor middle note” and “end note or dry-out”. Since odor perception largelyalso depends on odor intensity, the head note of a perfume or fragrancedoes not solely consist of highly volatile compounds, while the end notelargely consists of less volatile, i.e. tenacious odoriferoussubstances. When formulating perfumes, more highly volatile odoriferoussubstances may, for example, be bound to certain fixatives, sopreventing them from vaporizing rapidly. Accordingly, in the followingclassification of odoriferous substances into “more highly volatile” or“tenacious” odoriferous substances, no statement is made about odorimpression nor about whether the corresponding odoriferous substance isperceived as a top or heart note.

Appropriate selection of the stated fragrances or perfume oils may inthis manner have an influence on the agents according to the inventionboth in terms of product odor immediately on opening the brand new agentand in terms of the odor in service, for example during use in adishwashing machine. These odor impressions may, of course, beidentical, but may also differ. It is advantageous to use more tenaciousodoriferous substances for the latter odor impression, while more highlyvolatile odoriferous substances may also be used for productfragrancing. Tenacious odoriferous substances which may be used for thepurposes of the present invention are, for example, essential oils suchas angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil,bergamot oil, champak flower oil, silver fir oil, silver fir cone oil,elemi oil, eucalyptus oil, fennel oil, pine-needle oil, galbanum oil,geranium oil, ginger grass oil, guaiacwood oil, gurjun balsam oil,helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calmus oil,camomile oil, camphor oil, canaga oil, cardamom oil, cassia oil, pineneedle oil, copaiva balsam oil, coriander oil, spearmint oil, carawayoil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil,melissa oil, ambrette oil, myrrh oil, clove oil, neroli oil, niaoulioil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchoulioil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil,pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celeryoil, spike oil, star anise oil, terpentine oil, thuja oil, thyme oil,verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreenoil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil,citronellol, lemon oil and cypress oil. Higher-boiling or solidodoriferous substances of natural or synthetic origin may, however, alsobe used for the purposes of the present invention as tenaciousodoriferous substances or odoriferous substance mixtures, i.e.fragrances. These compounds include the compounds stated below andmixtures thereof, ambrettolide, α-amylcinnamaldehyde, anethole,anisaldehyde, anisyl alcohol, anisole, anthranilic acid methyl ester,acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester,benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzylformate, benzyl valerate, borneol, bornyl acetate, α-bromostyrene,n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether,eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate,geranyl formate, heliotropin, methyl heptine carbonate, heptaldehyde,hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamylalcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrole,jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin,p-methoxyacetophenone, methyl N-amyl ketone, methylanthranilic acidmethyl ester, p-methylacetophenone, methylchavicol, p-methylquinoline,methyl-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonylketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol,nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde,p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol,phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone,safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate,cyclohexyl salicylate, santalol, skatole, terpineol, thymene, thymol,γ-undecalactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamylalcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. More highlyvolatile odoriferous substances include in particular lower-boilingodoriferous substances of natural or synthetic origin, which may be usedalone or in mixtures. Examples of more highly volatile odoriferoussubstances are alkyl isothiocyanates (alkyl mustard oils), butanedione,limonene, linalool, linalyl acetate and propionate, menthol, menthone,methyl n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate,citral, citronellal.

The plastics particles are preferably loaded with the selected fragranceat a temperature of 15 to 30° C., preferably of 20 to 25° C. To thisend, the particles are combined with the appropriate quantity offragrance and intermixed. In any event, however, the temperature shouldbe below the melting or decomposition temperature of the plastic andalso below the flash point of the perfume oil. The fragrance isprimarily taken up by the polymeric support material or by furtherperfume support materials contained in the particle by adhesion,diffusion and/or capillary forces, said support materials possiblyswelling slightly over the course of this procedure.

Further Active Substances

As previously mentioned, agents according to the invention may containfurther active substances apart from the constituents necessary forfragrancing and deodorization. Further product groups which containfurther preferred substances in addition to the above-statedconstituents according to the invention may accordingly bedifferentiated from agents which serve solely for fragrancing.

Dyes

Dyes are the first kind of these optionally usable preferred substances.Dyes which are suitable for this purpose are any dyes which are known toa person skilled in the art to be suitable for coloring plastics or aresoluble in perfume oils. It is preferred to select the dye in accordancewith the fragrance used; for example particles with a lemon odor willpreferably have a yellow color, while a green color is preferred forparticles with an apple or herbal fragrance. Preferred dyes haveelevated storage stability and are insensitive to the other constituentsof the agents and to light. If the agents according to the invention areused in connection with cleaning textiles or dishes, the dyes usedshould not have any pronounced substantivity towards textile fibers,glass, plastic dishes or ceramics so that they do not color such items.

Suitable dyes and dye mixtures are commercially obtainable under varioustrade names and are offered for sale inter alia by the companies BASFAG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStarTextilfarben GmbH & Co. Deutschland KG, Les Colorants Wackherr SA andCiba Specialty Chemicals. Suitable fat-soluble dyes and dye mixturesinclude, for example, Solvent Blue 35, Solvent Green 7, Solvent Orange 1(Fat Orange W-2201), Sandoplast Blue 2B, Fat Yellow 3G, Iragon® Red SRE122, Iragon® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, butother dyes may also be present.

In a preferred embodiment, the dye not only has an aesthetic effect butalso serves an indicator function. In this manner, the consumer isinformed of the current state of consumption of the deodorant, so that,in addition to the absence of odor, which may for example also be due tohabituation on the part of the user, he/she receives an additionalreliable indication of when a deodorant has to be replaced with a newone.

The indicator action may be achieved in various different ways: on theone hand, a dye may be used which escapes from the particles over thecourse of use. This may be brought about, for example, by constituentspresent in the dishwashing detergent. To this end, a dye must be usedwhich adheres well to the particles or only slowly diffuses outtherefrom, in order to ensure that decolorization is not completed toosoon, namely before the fragrance has been consumed. On the other hand,however, a color change may be brought about by a chemical reaction orthermal decomposition.

Antimicrobial Active Ingredients, Germicides, Fungicides

Further preferred constituents of agents according to the invention aresubstances such as antimicrobial active ingredients, germicides,fungicides, antioxidants or corrosion inhibitors, with the assistance ofwhich additional benefits, such as for example disinfection or corrosionprotection, may be achieved.

The agents according to the invention may contain antimicrobial activeingredients in order to combat microorganisms. In this connection, adistinction is drawn, depending on the antimicrobial spectrum andmechanism of action, between bacteriostatics and bactericides,fungistatics and fungicides etc. Significant substances from thesegroups are, for example, benzalkonium chlorides, alkylarylsulfonates,halophenols and phenol mercuriacetate.

Antioxidants

The agents may contain antioxidants in order to prevent unwanted changesto the agents according to the invention or to the, for example, treatedtextiles brought about by the action of oxygen and other oxidativeprocesses. This class of compounds includes, for example, substitutedphenols, hydroquinones, pyrocatechols and aromatic amines as well asorganic sulfides, polysulfides, dithiocarbamates, phosphites andphosphonates.

If the agents according to the invention are used in dishwashingmachines, said agents may contain corrosion inhibitors to protect thearticles being washed or the machine, with silver protection agentsbeing of particular significance in relation to machine dishwashing.Known prior art substances may be used. In general, silver protectionagents which may be used are those primarily selected from the group oftriazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles,alkylaminotriazoles and transition metal salts or complexes.Benzotriazole and/or alkylaminotriazole are particularly preferablyused. Detergent formulations furthermore frequently comprise agentscontaining active chlorine which are capable of distinctly reducingcorrosion of silver surfaces. Organic redox-active compounds containingoxygen and nitrogen, such as di- and trihydric phenols, for examplehydroquinone, pyrocatechol, hydroxyhydroquinone, gailic acid,phloroglucinol, pyrogallol or derivatives of these classes of compoundsare in particular used in chlorine-free detergents. Saline and complexedinorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co andCe are also frequently used. Preferred compounds are here transitionmetal salts, which are selected from the group of manganese and/orcobalt salts and/or complexes, particularly preferably the cobalt(ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl)complexes, the chlorides of cobalt or manganese and of manganesesulfate. Zinc compounds may likewise by used to prevent corrosion of thearticles being washed.

Instead of or in addition to the above-described silver protectionagents, for example benzotriazoles, it is possible to use redox-activesubstances in the agents according to the invention. These substancesare preferably inorganic redox-active substances from the groupcomprising manganese, titanium, zirconium, hafnium, vanadium, cobalt andcerium salts and/or complexes, the metals preferably being present inone of oxidation numbers II, III, IV, V, or VI.

The metal salts or metal complexes used should be at least partiallysoluble in water. Counterions suitable for salt formation include notonly any conventional mono-, di- or trinegatively charged inorganicanions, for example oxide, sulfate, nitrate, fluoride, but also organicanions such as for example stearate.

Metal complexes for the purposes of the invention are compounds whichconsist of a central atom and one or more ligands and optionallyadditionally one or more of the above-mentioned anions. The central atomis one of the above-mentioned metals in one of the above-mentionedoxidation numbers. The ligands are neutral molecules or anions which aremono- or polydentate; the term “ligands” is explained in greater detailfor the purposes of the invention for example in “Römpp Chemie Lexikon,Georg Thieme Verlag Stuttgart/New York, 9th edition, 1990, page 2507”.If the charge of the central atom and the charge of the ligand(s) doesnot add up to zero in a metal complex, either one or more of theabove-mentioned anions or one or more cations, for example sodium,potassium or ammonium ions, ensures charge equalization depending onwhether a cationic or an anionic charge surplus is present. Examples ofsuitable complexing agents are citrate, acetylacetonate or1-hydroxyethane-1,1-diphosphonate.

The chemically familiar definition of “oxidation number” is given forexample in “Römpp Chemie Lexikon, Georg Thieme Veriag Stuftgart/NewYork, 9th edition, 1991, page 3168”.

Particularly preferred metal salts and/or metal complexes are selectedfrom the group comprising MnSO₄, Mn(II) citrate, Mn(II) stearate, Mn(II)acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄,VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃ and mixturesthereof such that preferred agents according to the invention arecharacterized in that the metal salts and/or metal complexes areselected from the group comprising MnSO₄, Mn(II) citrate, Mn(II)stearate, Mn(II) acetylacetonate, Mn(II)[1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆,K₂ZrF₆, CoSO₄, CO(NO₃)₂, Ce(NO₃)₃.

These metal salts or metal complexes generally comprise conventionalcommercial substances, which may be used to protect silver againstcorrosion without prior cleaning in the agents according to theinvention. Thus, the mixture known from SO₃ production (contact method)of pentavalent and tetravalent vanadium (V₂O₅, VO₂, V₂O₄) is suitable,for example, as is the titanyl sulfate, TiOSO₄, arising through dilutionof a Ti(SO₄) solution.

The stated metal salts and/or metal complexes are contained in theagents according to the invention preferably in a quantity of from 0.05to 6 wt. %, preferably 0.2 to 2.5 wt. %, relative to the total agentwithout the container.

Agents for Preventing Glass Corrosion

In addition to the cleaning performance thereof, one important criterionfor assessing a machine dishwashing detergent is the visual appearanceof the dry dishes after cleaning has been performed. Any calciumcarbonate deposits which may occur on dishes or inside the machine mayhave a disadvantageous effect on customer satisfaction, for example, andthus have a causal influence on the economic success of such a cleaningagent. A further long-standing problem of machine dishwashing iscorrosion of glassware, which generally takes the form not only ofcloudiness, streaks and scratches, but also of iridescence of the glasssurface. The observed effects are the result substantially of twoprocesses, on the one hand the discharge of alkali and alkaline earthions from the glass in conjunction with hydrolysis of the silicatenetwork and on the other hand the deposition of silicate compounds onthe glass surface.

The stated problems may be solved with the agents according to theinvention if, in addition to the above-stated compulsory and optionalconstituents, specific glass corrosion inhibitors are incorporated intothe agents. Preferred agents according to the invention thereforeadditionally contain one or more magnesium and/or zinc salts and/ormagnesium and/or zinc complexes.

A preferred class of compounds, which may be added to the agentsaccording to the invention to prevent glass corrosion, are insolublezinc salts. These may attach themselves to the surface of the glassduring the dishwashing process and there prevent the dissolution ofmetal ions from the glass network and hydrolysis of the silicates. Inaddition, these insoluble zinc salts also prevent the deposition ofsilicate on the glass surface, such that the glass is protected from theabove-described consequences.

For the purposes of this preferred embodiment, insoluble zinc salts arezinc salts which have a solubility of at most 10 grams of zinc salt perliter of water at 20° C. Examples of insoluble zinc salts particularlypreferred according to the invention are zinc silicate, zinc carbonate,zinc oxide, basic zinc carbonate (Zn₂(OH)₂CO₃), zinc hydroxide, zincoxalate, zinc monophosphate (Zn₃(PO₄)₂), and zinc pyrophosphate(Zn₂(P₂O₇)).

The stated zinc compounds are used in the agents according to theinvention in quantities which bring about a zinc ion content in theagents of between 0.02 and 10 wt. %, preferably between 0.1 and 5.0 wt.% and in particular between 0.2 and 1.0 wt. %, in each case relative tothe agent without the container. The exact zinc salt content of theagent is naturally dependent on the zinc salt type the lower thesolubility of the zinc salt used, the higher should be the concentrationthereof in the agents according to the invention.

A further preferred class of compounds comprises magnesium and/or zincsalt(s) of at least one monomeric and/or polymeric organic acid. Thesehave the effect that, even with repeated use, the surfaces of glasswareare not changed corrosively, in particular no clouding, streaks orscratching are caused, and also no iridescence of the glass surfaces.

Although, according to the invention, any magnesium and/or zinc salt(s)of monomeric and/or polymeric organic acids may be contained in theclaimed agents, as described above preference is given to the magnesiumand/or zinc salts of monomeric and/or polymeric organic acids from thegroups comprising unbranched saturated or unsaturated monocarboxylicacids, branched saturated or unsaturated monocarboxylic acids, saturatedand unsaturated dicarboxylic acids, aromatic mono-, di- andtricarboxylic acids, saccharic acids, hydroxy acids, oxo acids, aminoacids and/or polymeric carboxylic acids. Within these groups, for thepurposes of the present invention the acids stated below are in turnpreferred:

The spectrum of zinc salts preferred according to the invention oforganic acids, preferably organic carboxylic acids, extends from saltswhich are sparingly soluble or insoluble in water, i.e. exhibit asolubility of below 100 mg/L, preferably below 10 mg/L, in particular nosolubility, up to those salts which display a solubility in water ofabove 100 mg/L, preferably above 500 mg/L, particularly preferably above1 g/L and in particular above 5 g/L (all solubilities at 20° C. watertemperature). The first group of zinc salts includes for example zinccitrate, zinc oleate and zinc stearate, the group of soluble zinc saltsincluding for example zinc formate, zinc acetate, zinc lactate and zincgluconate:

In a further preferred embodiment of the present invention, the agentsaccording to the invention contain at least one zinc salt, but nomagnesium salt, of an organic acid, the at least one zinc saltpreferably being a zinc salt of an organic carboxylic acid, particularlypreferably a zinc salt from the group comprising zinc stearate, zincoleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate.Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.

An agent preferred for the purposes of the present invention containszinc salt in quantities of from 0.1 to 5 wt. %, preferably of from 0.2to 4 wt. % and in particular of from 0.4 to 3 wt. %, or zinc in oxidizedform (calculated as Zn²⁺) in quantities of from 0.01 to 1 wt. %,preferably of from 0.02 to 0.5 wt. % and in particular of from 0.04 to0.2 wt. %, in each case relative to the agent without the container.

The present application accordingly also preferably provides a fragrancerelease system, which contains further active substances, in particularactive substances from the group comprising perfume carriers, dyes,antimicrobial active ingredients, germicides, fungicides, antioxidantsor corrosion inhibitors.

Bleaching Agents

In addition to the above-stated active substances, the agents accordingto the invention, in particular agents for use in dishwashing machines,textile washing machines or dryers, may of course comprise all activesubstances conventionally contained in agents for cleaning textiles ordishes or for textile or dish care, particular preference being given tosubstances from the group comprising bleaching agents, bleachingactivators, polymers, builders, surfactants, enzymes, electrolytes, pHadjusting agents, fragrances, perfume carriers, dyes, hydrotropes, foaminhibitors, antiredeposition agents, optical brighteners, grayinginhibitors, shrinkage prevention agents, anti-crease agents, dyetransfer inhibitors, antimicrobial active ingredients, germicides,fungicides, antioxidants, corrosion inhibitors, antistatic agents,waterproofing and impregnation agents, anti-swelling and anti-slipagents, nonaqueous solvents, rinse conditioners, protein hydrolysates,and UV absorbers. Such combination products are then, in addition torepeated fragrancing, also suitable for single or repeated care orcleaning of textiles or dishes.

Bleaching agents and bleaching activators may be present in the agentsaccording to the invention as important constituents of detergents orcleaning agents in addition to other constituents Among those compoundsacting as bleaching agents which release H₂O₂ in water, sodium perboratetetrahydrate and sodium perborate monohydrate are of particularsignificance. Further usable bleaching agents are, for example, sodiumpercarbonate, peroxypyrophosphates, citrate perhydrates andH₂O₂-releasing per-acidic salts or per-acids, such as perbenzoates,peroxophthalates, diperazelaic acid, phthaloimino per-acid ordiperdodecanedioic acid. Detergent moldings for machine dishwashing mayalso contain bleaching agents from the group of organic bleachingagents. Typical organic bleaching agents are diacyl peroxides, such asfor example dibenzoyl peroxide. Further typical organic bleaching agentsare peroxy acids, with examples which may in particular be mentionedbeing alkylperoxy acids and arylperoxy acids. Preferred representativeswhich may be used are (a) peroxybenzoic acid and the ring-substitutedderivatives thereof, such as alkylperoxybenzoic acids, as well asperoxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic orsubstitutedly aliphatic peroxy acids, such as peroxylauric acid,peroxystearic acid, E-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproicacid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and(c) aliphatic and araliphatic peroxydicarboxylic acids, such as1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacicacid, diperoxybrassylic acid, diperoxyphthalic acids,2-decyldiperoxybutane-1,4-dioic acid,N,N-terephthaloyldi(6-aminopercaproic acid).

If the agents according to the invention are used in combination withmachine dishwashing detergents, the latter may contain bleachingactivators in order to achieve an enhanced bleaching action whencleaning at temperatures of 60° C. and below. Bleaching activators whichmay be used are compounds which, under perhydrolysis conditions, yieldaliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, inparticular 2 to 4 C atoms, and/or optionally substituted perbenzoicacid. Suitable substances are those which bear O- and/or N-acyl groupshaving the stated number of C atoms and/or optionally substitutedbenzoyl groups. Preferred compounds are repeatedly acylatedalkylenediamines, in particular tetraacetylethylenediamine (TAED),acylated triazine derivatives, in particular1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylatedglycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides,in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates,in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- oriso-NOBS), carboxylic anhydrides, in particular phthalic anhydride,acylated polyhydric alcohols, in particular triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran.

Further bleaching activators which are preferably used for the purposesof the present application are compounds from the group of cationicnitriles, in particular cationic nitrites of the formula

in which R¹ denotes —H, —CH₃, a C₂₋₂₄ alkyl or alkenyl residue, asubstituted C₂₋₂₄ alkyl or alkenyl residue with at least one substituentfrom the group —Cl, —Br, —OH, —NH₂, —CN, an alkyl or alkenylaryl residuewith a C₁₋₂₄ alkyl group, or denotes a substituted alkyl or alkenylarylresidue with a C₁₋₂₄ alkyl group and at least one further substituent onthe aromatic ring, R² and R³ are mutually independently selected from—CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH,—CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃,—CH(OH)—CH₂—CH₃, —(CH₂CH₂—O)_(n)H with n=1, 2, 3, 4, 5 or 6 and X is ananion.

Particularly preferred agents according to the invention contain acationic nitrite of the formula

in which R⁴, R⁵ and R⁶ are mutually independently selected from —CH₃,—CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, wherein R⁴ may additionally alsobe —H and X is an anion, wherein preferably R⁵=R⁶=—CH₃ and in particularR⁴═R⁵=R⁶=—CH₃ and compounds of the formulae (CH₃)₃N⁽⁺⁾CH₂—CNX⁻,(CH₃CH₂)₃N⁽⁺⁾CH₂—CNX⁻, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂—CNX⁻,(CH₃CH(CH₃))₃N⁽⁺⁾CH₂—CNX⁻, or (HO—CH₂—CH₂)₃N⁽⁺⁾CH₂—CNX⁻ are particularlypreferred, wherein in turn from the group of these substances thecationic nitrile of the formula (CH₃)₃N⁽⁺⁾CH₂—CNX⁻, in which X⁻ denotesan anion which is selected from the group chloride, bromide, iodide,hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) orxylenesulfonate, is particularly preferred.

In addition to conventional bleaching activators or instead of them, itis also possible to incorporate “bleach catalysts” into the agents.These substances comprise bleach-boosting transition metal salts ortransition metal complexes such as for example Mn, Fe, Co, Ru or Mosalen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cucomplexes with nitrogenous tripod ligands and Co, Fe, Cu and Ru amminecomplexes may also be used as bleach catalysts.

Surfactants

For the purposes of the present application, preferred agents containone or more surfactant(s) from the groups of anionic, nonionic, cationicand/or amphoteric surfactants.

Preferably used anionic surfactants in acid form are one or moresubstances from the group comprising carboxylic acids, sulfuric acidsemiesters and sulfonic acids, preferably from the group comprisingfatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids Ifthey are to exhibit adequate surface-active properties, the statedcompounds should here comprise relatively long-chain hydrocarbonresidues, thus at least 6 C atoms in the alkyl or alkenyl residue. The Cchain distributions of anionic surfactants are conventionally in therange from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbonatoms.

Carboxylic acids which are used in the form of their alkali metal saltsas soaps in detergents and cleaning agents are largely obtainedindustrially from native fats and oils by hydrolysis. While alkalinesaponification, which was carried out as long ago as last century, gaverise directly to alkali metal salts (soaps), today only water, whichcleaves the fats into glycerol and free fatty acids, is used forcleavage on a large industrial scale. Processes which are used on alarge industrial scale are for example autoclave cleavage or continuoushigh pressure cleavage. Carboxylic acids usable in acid form for thepurposes of the present invention as anionic surfactants are for examplehexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoicacid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid(capric acid), undecanoic acid etc. It is preferred for the purposes ofthe present compound to use fatty acids such as dodecanoic acid (lauricacid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmiticacid), octadecanoic acid (stearic acid), eicosanoic acid (arachidicacid), docosanoic acid (behenic acid), tetracosanoic acid (lignocericacid), hexacosanoic acid (cerotic acid), triacontanoic acid (melissicacid) and the unsaturated species 9c-hexadecenoic acid (palmitoleicacid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid(petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoicacid (elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid),9t,12t-octadecadienoic acid (linolaidic acid) and9c,12c,15c-octadecatrienoic acid (linolenic acid). It is preferred oncost grounds not to use the pure species, but instead technical mixturesof the individual acids, as are obtainable from fat cleavage. Suchmixtures are for example coconut oil fatty acid (approx. 6 wt. % C₈, 6wt. % C₁₀, 48 wt. % C₁₂, 18 wt. % C₁₁, 10 Wt. % C₁₆, 2 wt. % C₁₈, 8 wt.% C_(18′), 1 wt. % C_(18″)), palm kernel oil fatty acid (approx. 4 wt. %C₈, 5 Wt. % C₁₀, 50 wt. % C₁₂, 15 Wt. % C₁₄, 7 wt. % C₁₆, 2 wt. % C₁₈,15 wt. % C_(18′), 1 wt. % C_(18″)), tallow fatty acid (approx. 3 wt. %C₁₄, 26 wt. % C₁₆, 2 wt. % CO₅₆, 2 wt. % C₁₇, 17 wt. % C₁₈, 44 wt. %C_(18′), 3 wt. % C_(18″), 1 wt. % C₁₈), hydrogenated tallow fatty acid(approx. 2 wt. % C₁₄, 28 wt. % C₁₆, 2 wt. % C₁₇, 63 wt. % C₁₈, 1 wt. %C₁₈″), technical oleic acid (approx. 1 wt. % C₁₂, 3 wt. % C₁₄, 5 wt. %C₁₆, 6 wt. % C_(16′), 1 Wt. % C₁₇, 2 wt. % C₁₈, 70 wt. % C_(18′), 10 wt.% C_(18″), 0.5 wt. % C_(18′″)), technical palmitic/stearic acid (approx.1 wt. % C₁₂, 2 wt. % C₁₄, 45 wt. % C₁₆, 2 wt. % C₁₇, 47 wt. % C₁₈, 1 wt.% C_(18′)) and soybean oil fatty acid (approx. 2 wt. % C₁₄, 15 wt. %C₁₆, 5 wt. % C₁₈, 25 wt. % C_(18′), 45 wt. % C_(18″), 7 wt. % C_(18′″)).

Sulfuric acid semiesters of relatively long-chain alcohols are likewiseanionic surfactants in their acid form and are usable for the purposesof the present invention. Their alkali metal salts, in particular sodiumsalts, namely fatty alcohol sulfates, are obtainable on a largeindustrial scale from fatty alcohols which are reacted with sulfuricacid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide toyield the corresponding alkylsulfuric acid and are subsequentlyneutralized. The fatty alcohols are here obtained from the correspondingfatty acids or fatty acid mixtures by high pressure hydrogenation of thefatty acid methyl esters. The most significant industrial process involume terms for producing fatty alkylsulfuric acids is sulfonation ofthe alcohols with SO₃/air mixtures in special cascade, failing-film ortube-bundle reactors.

Another class of anionic surfactant acids which may be used according tothe invention are alkyl ether sulfuric acids, the salts thereof, alkylether sulfates, which, in comparison with alkyl sulfates, aredistinguished by higher water solubility and lower sensitivity to waterhardness (solubility of Ca salts). Alkyl ether sulfuric acids aresynthesized in the same manner as alkylsulfuric acids from fattyalcohols which are reacted with ethylene oxide to yield thecorresponding fatty alcohol ethoxylates. Propylene oxide may also beused instead of ethylene oxide. Subsequent sulfonation with gaseoussulfur trioxide in short retention time sulfonation reactors providesyields of above 98% of the corresponding alkyl ether sulfuric acids.

Alkanesulfonic acids and olefinsulfonic acids may also be used for thepurposes of the present invention as anionic surfactants in acid form.Alkanesulfonic acids may contain the sulfonic acid group attachedterminally (primary alkanesulfonic acids) or along the C chain(secondary alkanesulfonic acids), with only secondary alkanesulfonicacids being of commercial significance. These are produced bysulfochlorination or sulfoxidation of linear hydrocarbons. In Reedsulfochlorination, n-paraffins are reacted with sulfur dioxide andchlorine under UV light irradiation to yield the correspondingsulfochlorides which, when hydrolyzed with alkalis, directly give riseto alkane sulfonates and, on reaction with water, give rise toalkanesulfonic acids. Since di- and polysulfochlorides and chlorinatedhydrocarbons may occur as secondary products of the free-radicalreaction during sulfochlorination, the reaction is conventionallycarried out only up to a degree of conversion of 30% and thenterminated.

Another process for producing alkanesulfonic acids is sulfoxidation, inwhich n-paraffins are reacted with sulfur dioxide and oxygen under UVlight irradiation. This free-radical reaction yields successivealkylsulfonyl radicals which react further with oxygen to yieldalkylpersulfonyl radicals. The reaction with an unreacted paraffinyields an alkyl radical and the alkylpersulfonic acid, which breaks downinto an alkylperoxysulfonyl radical and a hydroxyl radical. The reactionof the two free radicals with an unreacted paraffin yields alkylsulfonicacids and water, which reacts with alkylpersulfonic acid and sulfurdioxide to yield sulfuric acid. In order to keep the yield of the twofinal products alkylsulfonic acid and sulfuric acid as high as possibleand to suppress secondary reactions, this reaction is conventionallycarried out only up to a degree of conversion of 1% and then terminated.

Olefin sulfonates are produced industrially by reaction of α-olefinswith sulfur trioxide. This results in the intermediate formation ofzwitterions which cyclize to yield “sultones”. Under suitable conditions(alkaline or acid hydrolysis), these sultones react to yieldhydroxylalkanesulfonic acids or alkenesulfonic acids, which may bothlikewise be used as anionic surfactant acids.

Alkylbenzenesulfonates have been known as high-performance anionicsurfactants since the 1930s. At that time, alkylbenzenes were producedby monochlorination of Kogasin fractions and subsequent Friedel-Craftsalkylation, the alkylbenzenes then being sulfonated with oleum andneutralized with sodium hydroxide. In the early 1950s,alkylbenzenesulfonates were produced by tetramerizing propylene to yieldbranched α-dodecylene, and the product was converted via aFriedel-Crafts reaction, using aluminum trichloride or hydrogenfluoride, to tetrapropylene benzene, which was then sulfonated andneutralized. This economical capability for producing tetrapropylenebenzenesulfonates (TPS) led to a breakthrough for this surfactant class,which subsequently displaced soaps as the main surfactant in detergentsand cleaning agents.

Due to the inadequate biodegradability of TPS, the need arose to providenew alkylbenzenesulfonates which were characterized by betterenvironmental behavior. These requirements have been met by linearalkylbenzenesulfonates, which today are almost the onlyalkylbenzenesulfonates produced, and are abbreviated ABS or LAS.

Linear alkylbenzenesulfonates are produced from linear alkylbenzenes,which are in turn obtainable from linear olefins. This is done on alarge industrial scale by separating petroleum fractions with molecularsieves into n-paraffins of the desired purity, and dehydrogenating themto yield n-olefins, resulting in both α- and i-olefins. The resultantolefins are then reacted with benzene, in the presence of acidcatalysts, to yield alkylbenzenes, the Friedel-Crafts catalyst selectedhaving an influence on the isomer distribution of the resulting linearalkylbenzenes: if aluminum trichloride is used, the content of 2-phenylisomers in the mixture with 3-, 4-, 5-, and other isomers is about 30 wt%, while if hydrogen fluoride is used as the catalyst, the 2-phenylisomer content can be reduced to approx. 20 wt. %. Lastly, sulfonationof linear alkylbenzenes is performed today on a large industrial scalewith oleum, sulfuric acid, or gaseous sulfur trioxide, the latter beingby far the most significant, Sulfonation is carried out using specialfilm or tube-bundle reactors which yield a 97 wt. % alkylbenzenesulfonicacid (ABSA) as product, which may be used for the purposes of thepresent invention as an anionic surfactant acid.

By selection of the neutralizing agent, it is possible to obtain a verywide variety of salts, i.e. alkylbenzenesulfonates, from ABSA. Forreasons of economy, it is preferred in this context to produce and usethe alkali metal salts, and among these preferably the sodium salts, ofABSA. These can be described by the general formula IX:

in which the sum of x and y is conventionally between 5 and 13. C₈₋₁₆,preferably C₉₋₁₃, alkylbenzenesulfonic acids are preferably usedaccording to the invention as an anionic surfactant in acid form. It isfurther preferred for the purposes of the present invention to useC₈₋₁₆, preferably C₉₋₁₃ alkylbenzenesulfonic acids which are derivedfrom alkylbenzenes having a tetralin content of less than 5 wt. %relative to the alkylbenzene. It is further preferred to usealkylbenzenesulfonic acids whose alkylbenzenes have been produced by theHF process, such that the C₈₋₁₆, preferably C₉₋₁₃ alkylbenzenesulfonicacids used have a 2-phenyl isomer content of below 22 wt. % relative tothe alkylbenzenesulfonic acid.

The above-stated anionic surfactants may be used in their acid formalone or mixed with one another. It is, however, also possible andpreferred for further, preferably acidic, constituents of detergents andcleaning agents to be incorporated in quantities of from 0.1 to 40 wt.%, preferably of from 1 to 15 wt. % and in particular of from 2 to 10wt. %, in each case relative to the weight of the mixture to be reacted,into the anionic surfactant in acid form prior to addition onto thesupport material(s).

It is, of course, also possible to use the anionic surfactants inpartially or completely neutralized form. These salts may then bepresent in the granulation liquid not only as a solution, suspension oremulsion, but also as a solid constituent of the solids bed. Cations forsuch anionic surfactants which may be considered, apart from alkalimetals (here in particular salts as claimed and K salts), are ammoniumas well as mono-, di-, or triethanolalkonium ions. Instead of mono-,di-, or triethanolamine, it is possible for the analogousrepresentatives of mono-, di-, or trimethanolamine, or those of thealkanolamines of higher alcohols to be quaternized and present as acation.

Cationic surfactants may also advantageously be used as the activesubstance. The cationic surfactant may here be added directly to themixer in its form as delivered, or be sprayed onto the solid supports inthe form of a liquid to pasty cationic surfactant preparation. Suchcationic surfactant preparations may be produced, for example, by mixingconventional commercial cationic surfactants with auxiliary substancessuch as nonionic surfactants, polyethylene glycols or polyols. Loweralcohols such as ethanol and isopropanol may also be used, in which casethe quantity of such lower alcohols in the liquid cationic surfactantpreparation should be below 10 wt. % for the above-stated reasons.

Cationic surfactants which may be considered for the agents according tothe invention are any conventional substances, with cationic surfactantshaving a textile-softening action being distinctly preferred.

The agents according to the invention may contain one or more cationictextile-softening agents of the formulae X, XI or XII as cationic activesubstances having a textile-softening action:

in which each group R¹ is mutually independently selected from amongC₁₋₆ alkyl, alkenyl or hydroxyalkyl groups; each group R² is mutuallyindependently selected from among C₈₋₂₈ alkyl or alkenyl groups; R³=R¹or (CH₂)_(n-)T-R²; R⁴=R¹ or R² or (CH₂)_(n-)T-R²; T=—CH₂—, —O—CO— or—CO—O— and n is an integer from 0 to 5.

In preferred embodiments of the present invention, the agentsadditionally contain nonionic surfactant(s) as an active substance.

Alkoxylated, advantageously ethoxylated, in particular primary alcoholswith preferably 8 to 18 C atoms and on average 1 to 12 mol of ethyleneoxide (EO) per mol of alcohol, in which the alcohol residue may belinear or preferably methyl-branched in position 2 or may contain linearand methyl-branched residues in the mixture, as they are usually presentin oxo alcohol residues, are preferably used as nonionic surfactants. Inparticular, however, alcohol ethoxylates with linear residues preparedfrom alcohols of natural origin with 12 to 18 C atoms, for example fromcoconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO permol of alcohol are preferred. Preferred ethoxylated alcohols include,for example, C₁₂₋₁₄ alcohols with 3 EO or 4 EO, C₉₋₁₁ alcohols with 7EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C₁₂₋₁₈ alcohols with3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C₁₂₋₁₄alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5 EO. The stated degrees ofethoxylation are statistical averages which, for a specific product, maybe an integer or a fractional number. Preferred alcohol ethoxylates havea narrow homologue distribution (narrow range ethoxylates, NRE). Inaddition to these nonionic surfactants, fatty alcohols with more than 12EO may also be used. Examples of these are tallow fatty alcohol with 14EO, 25 EO, 30 EO or 40 EO.

Alkylglycosides of the general formula RO(G)_(x), in which R means aprimary straight-chain or methyl-branched aliphatic residue, inparticular methyl-branched in position 2, with 8 to 22, preferably 12 to18 C atoms and G is the symbol which denotes a glycose unit with 5 or 6C atoms, preferably glucose, may moreover be used as further nonionicsurfactants. The degree of oligomerization x, which indicates thedistribution of monoglycosides and oligoglycosides, is any desirednumber between 1 and 10; x is preferably 1.2 to 1.4.

A further class of preferably used nonionic surfactants, which may beused either as the sole nonionic surfactant or in combination with othernonionic surfactants, are alkoxylated, preferably ethoxylated orethoxylated and propoxylated fatty acid alkyl esters, preferably with 1to 4 carbon atoms in the alkyl chain, in particular fatty acid methylesters.

Nonionic surfactants of the amine oxide type, for example N-coconutalkyl-N,N-dimethylamine oxide and N-tallowalcohol-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamidetype may also be suitable. The quantity of these nonionic surfactantspreferably amounts to no more than that of the ethoxylated fattyalcohols, in particular no more than half the quantity thereof.

Further suitable surfactants are polyhydroxyfatty acid amides of theformula XIII,

in which RCO denotes an aliphatic acyl residue with 6 to 22 carbonatoms, R¹ denotes hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4carbon atoms and [Z] denotes a linear or branched polyhydroxyalkylresidue with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Thepolyhydroxyfatty acid amides comprise known substances which mayconventionally be obtained by reductive amination of a reducing sugarwith ammonia, an alkylamine or an alkanolamine and subsequent acylationwith a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxyfatty acid amides also includes compounds of theformula XIV,

in which R denotes a linear or branched alkyl or alkenyl residue with 7to 12 carbon atoms, R¹ denotes a linear, branched or cyclic alkylresidue or an aryl residue with 2 to 8 carbon atoms and R² denotes alinear, branched or cyclic alkyl residue or an aryl residue or anoxyalkyl residue with 1 to 8 carbon atoms, wherein C₁₋₄ alkyl or phenylresidues are preferred, and [Z] denotes a linear polyhydroxyalkylresidue, the alkyl chain of which is substituted with at least twohydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylatedderivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar,for example glucose, fructose, maltose, lactose, galactose, mannose orxylose. The N-alkoxy- or N-aryloxy-substituted compounds may then beconverted into the desired polyhydroxyfatty acid amides by reaction withfatty acid methyl esters in the presence of an alkoxide as catalyst.

It is particularly preferred for many applications for the ratio ofanionic surfactant(s) to nonionic surfactant(s) to amount to between10:1 and 1:10, preferably between 7.5:1 and 1:5 and in particularbetween 5:1 and 1:2, Containers according to the invention are herepreferred which contain surfactant(s), preferably anionic and/ornonionic surfactant(s), in quantities of from 5 to 80 wt. %, preferablyof from 7.5 to 70 wt. %, particularly preferably of from 10 to 60 wt. %and in particular of from 12.5 to 50 wt. %, in each case relative to theweight of the enclosed solids.

As has already been mentioned, the use of surfactants in cleaning agentsfor machine dishwashing is preferably limited to the use of smallquantities of nonionic surfactants. Agents according to the inventionfor machine dishwashing therefore preferably contain only specificnonionic surfactants which are described below. Only low-foamingnonionic surfactants are conventionally used as surfactants in machinedishwashing detergents. Representatives from the groups of anionic,cationic or amphoteric surfactants are, in contrast, of lesssignificance. Alkoxylated, advantageously ethoxylated, in particularprimary alcohols with preferably 8 to 18 C atoms and on average 1 to 12mol of ethylene oxide (EO) per mol of alcohol, in which the alcoholresidue may be linear or preferably methyl-branched in position 2 or maycontain linear and methyl-branched residues in the mixture, as they areusually present in oxo alcohol residues, are preferably used as nonionicsurfactants. In particular, however, alcohol ethoxylates with linearresidues prepared from alcohols of natural origin with 12 to 18 C atoms,for example from coconut, palm, tallow fat or oleyl alcohol, and onaverage 2 to 8 EO per mol of alcohol are preferred. Preferredethoxylated alcohols include, for example, C₁₂₋₁₄ alcohols with 3 EO or4 EO, C₉₋₁₁ alcohols with 7 EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or8 EO, C₁₂₋₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these,such as mixtures of C₁₂₋₁₄ alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5EO. The stated degrees of ethoxylation are statistical averages which,for a specific product, may be an integer or a fractional number.Preferred alcohol ethoxylates have a narrow homologue distribution(narrow range ethoxylates, NRE). In addition to these nonionicsurfactants, fatty alcohols with more than 12 EO may also be used.Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or40 EO.

In particular in the case of cleaning agents for machine dishwashing, itis preferred for these to contain a nonionic surfactant which has amelting point above room temperature, preferably a nonionic surfactantwith a melting point of above 20° C. Nonionic surfactants which arepreferably to be used have melting points of above 25° C., whilenonionic surfactants which are particularly preferably to be used havemelting points of between 25 and 60° C., in particular between 26.6 and43.3° C.

Suitable nonionic surfactants which have melting or softening points inthe stated temperature range are for example low-foaming nonionicsurfactants which may be solid or highly viscous at room temperature. Ifnonionic surfactants which are highly viscous at room temperature areused, it is preferred for them to have a viscosity of above 20 Pa·s,preferably of above 35 Pa·s and in particular of above 40 Pa·s. Nonionicsurfactants which have a waxy consistency at room temperature are alsopreferred.

Preferably used nonionic surfactants which are in solid form at roomtemperature originate from the groups of alkoxylated nonionicsurfactants, in particular ethoxylated primary alcohols and mixtures ofthese surfactants with structurally more complex surfactants such aspolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO)surfactants. Such (PO/EO/PO) nonionic surfactants are furthermoredistinguished by good foam control.

In one preferred embodiment of the present invention, the nonionicsurfactant with a melting point of above room temperature is anethoxylated nonionic surfactant which has been obtained from thereaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atomswith preferably at least 12 mol, particularly preferably at least 15mol, in particular at least 20 mol of ethylene oxide per mol of alcoholor alkylphenol.

One particularly preferred nonionic surfactant to be used, which issolid at room temperature, is obtained from a straight-chain fattyalcohol having 16 to 20 carbon atoms (C₁₆₋₂₀ alcohol), preferably a C₁₈alcohol and at least 12 mol, preferably at least 15 mol and inparticular at least 20 mol of ethylene oxide. Among these, the “narrowrange ethoxylates” (see above) are particularly preferred.

The nonionic surfactant which is solid at room temperature preferablyadditionally comprises propylene oxide units in its molecule. Such POunits preferably constitute up to 25 wt. %, particularly preferably upto 20 wt. % and in particular up to 15 wt. % of the entire molar mass ofthe nonionic surfactant. Particularly preferred nonionic surfactants areethoxylated monohydroxyalkanols or alkylphenols which additionallycomprise polyoxyethylene/polyoxypropylene block copolymer units. Thealcohol or alkylphenol moiety of such nonionic surfactant molecules herepreferably constitutes more than 30 wt. %, particularly preferably morethan 50 wt. % and in particular more than 70 wt. % of the entire molarmass of such nonionic surfactants.

Further nonionic surfactants with a melting point above room temperaturewhich are particularly preferably to be used contain 40 to 70% of apolyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend,which contains 75 wt. % of a reverse block copolymer of polyoxyethyleneand polyoxypropylene with 17 mol of ethylene oxide and 44 mol ofpropylene oxide and 25 wt. % of a block copolymer of polyoxyethylene andpolyoxypropylene, initiated with trimethylolpropane and containing 24mol of ethylene oxide and 99 mol of propylene oxide per mol oftrimethylolpropane.

Nonionic surfactants which may particularly preferably be used are forexample obtainable from Olin Chemicals under the name Poly TergenteSLF-18.

Another preferred surfactant may be described by the formula

R¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂0]_(y)[CH₂CH(OH)R²]

in which R¹ denotes a linear or branched aliphatic hydrocarbon residuewith 4 to 18 carbon atoms or mixtures thereof, R² denotes a linear orbranched hydrocarbon residue with 2 to 26 carbon atoms or mixturesthereof and x denotes values between 0.5 and 1.5 and y denotes a valueof at least 15.

Further preferably usable nonionic surfactants are the endgroup-terminated poly(oxyalkylated) nonionic surfactants of the formula

R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²

in which R¹ and R² denote linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R³denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or2-methyl-2-butyl residue, x denotes values between 1 and 30, k and jdenote values between 1 and 12, preferably between 1 and 5. If the valueof x is >2 each R³ in the above formula may be different. R¹ and R² arepreferably linear or branched, saturated or unsaturated, aliphatic oraromatic hydrocarbon residues with 6 to 22 carbon atoms, whereinresidues with 8 to 18 C atoms are particularly preferred. H, —CH₃ or—OH₂CH₃ are particularly preferred for the residue R³. Particularlypreferred values for x are in the range from 1 to 20, in particular from6 to 15.

As described above, each R³ in the above formula may be different if xis ≧2. In this manner, it is possible to vary the alkylene oxide unit inthe square brackets. For example, if x denotes 3, the residue R³ may beselected in order to form ethylene oxide (R³=H) or propylene oxide(R³=CH₃) units, which may be attached to one another in any sequence,for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO),(PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected hereby way of example and may perfectly well be larger, wherein the range ofvariation increases as the value of x rises and for example comprises alarge number of (EO) groups combined with a small number of (PO) groups,or vice versa.

Particularly preferred end group-terminated poly(oxyalkylated) alcoholsof the above-stated formula have values of k=1 and j=1, such that theabove formula may be simplified to

R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR²

In the latter-stated formula, R¹, R² and R³ are as defined above and xdenotes numbers from 1 to 30, preferably from 1 to 20 and in particularfrom 6 to 18. Particularly preferred surfactants are those in which theresidues R¹ and R² comprise 9 to 14 C atoms, R³ denotes H and x assumesvalues from 6 to 15.

Enzymes

Agents according to the invention may contain enzymes to enhance theirwashing or cleaning performance, it being in principle possible to useany enzymes established in the prior art for these purposes. Theseinclude in particular proteases, amylases, lipases, hemicellulases,cellulases or oxidoreductases, and preferably mixtures thereof. Theseenzymes are in principle of natural origin; starting from the naturalmolecules, improved variants are available for use in detergents andcleaning agents, said variants accordingly preferably being used. Agentsaccording to the invention preferably contain enzymes in totalquantities of 1×10⁻⁶ to 5 wt. % relative to active protein. Proteinconcentration may be determined with the assistance of known methods,for example the BCA method (bicinchonic acid;2,2′-biquinolyl-4,4′-dicarboxylic acid) or the biuret method.

Among proteases, those of the subtilisin type are preferred. Examples ofthese are subtilisins BPN′ and Carlsberg, protease PB92, subtilisins 147and 309, alkaline protease from Bacillus lentus, subtilisin DY and theenzymes thermitase, proteinase K and proteases TW3 and TW7, which areclassed among subtilases but not among the subtilisins as more narrowlydefined. Subtilisin Carlsberg is obtainable in a further developed formunder the trade name Alcalase® from Novozymes A/S, Bagsvasrd, Denmark.Subtilisins 147 and 309 are distributed under the trade name Esperase®,or Savinasee® by Novozymes. The variants sold under the name BLAP® arederived from the protease from Bacillus lentus DSM 5483.

Further usable proteases are for example the enzymes obtainable underthe trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®,Kannase® and Ovozymes® from Novozymes, those obtainable under the tradenames Purafect®, Purafect® 0xP and Properase® from Genencor, thatobtainable under the trade name Protosol® from Advanced BiochemicalsLtd., Thane, India, that obtainable under the trade name Wuxi® from WuxiSnyder Bioproducts Ltd., China, those obtainable under the trade namesProleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya,Japan, and that obtainable under the name Proteinase K-16 from KaoCorp., Tokyo, Japan.

Examples of amylases usable according to the invention are theα-amylases from Bacillus licheniformis, from B. amyloliquefaciens orfrom B. stearothermophilus and the further developments thereof enhancedfor use in detergents and cleaning agents. The enzyme from B.licheniformis is obtainable from Novozymes under the name Termamyl® andfrom Genencor under the name Purastar®ST. Further developed products ofthis α-amylase are obtainable from Novozymes under the trade nameDuramyl® and Termamyl® ultra, from Genencor under the name Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. Theα-amylase from B. amyloliquefaciens is distributed by Novozymes underthe name BAN®, and variants derived from the α-amylase from B.stearothermophilus are distributed under names BSG® and Novamyl®,likewise by Novozymes.

Note should moreover be taken for this purpose of the α-amylase fromBacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase(CGTase) from B. agaradherens (DSM 9948); fusion products of the statedmolecules may likewise be used.

Furthermore, the further developments of α-amylase from Aspergillusniger and A. oryzae obtainable under the trade name Fungamyl® fromNovozymes are also suitable. Another commercial product is for exampleAmylase-LT®.

Agents according to the invention may contain lipases or cutinases inparticular because of their triglyceride-cleaving activities, but alsoin order to produce peracids in situ from suitable precursors. Theseinclude, for example, lipases originally obtainable or further developedfrom Humicola lanuginosa (Thermomyces lanuginosus), in particular thosewith the D96L amino acid substitution. They are distributed, forexample, by Novozymes under the trade name Lipolase®, Lipolase® Ultra,LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases which wereoriginally isolated from Fusarium solanipisi and Humicola insolens are,for example, also usable. Lipases which are likewise usable areobtainable from Amano under the names Lipase CE®, Lipase P®, Lipase B®,or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, LipaseM-AP® and Lipase AML®. Lipases or cutinases from Genencor which may, forexample, be used are those whose initial enzymes were originallyisolated from Pseudomonas mendocina and Fusarium solanii. Furtherimportant commercial products which may be mentioned are thepreparations M1 Lipase® and Lipomax®, originally distributed byGist-Brocades, and the enzymes distributed by Meito Sangyo KK, Japan,under the names Lipase MY-30S, Lipase OF® and Lipase PL®, as may theproduct Lumafast® from Genencor.

In particular if they are intended for treating textiles, agentsaccording to the invention may contain cellulases, depending on theintended purpose as pure enzymes, as enzyme preparations or in the formof mixtures in which the individual components advantageously complementeach other with regard to their various performance characteristics.These performance characteristics in particular include contributions tothe primary or secondary washing performance of the agent(antiredeposition action or graying inhibition), to finishing (fabricaction) and even to the provision of a “stone washed” effect.

One usable fungal cellulase preparation with an elevated endoglucanase(EG) content or further developments thereof are offered for sale byNovozymes under the trade name Celluzyme. The products Endolase® andCarezyme® likewise obtainable from Novozymes are based on the 50 KD-EGor the 43 kD-EG from H. insolens DSM 1800. Further possible commercialproducts from this company are Cellusoft® and Renozyme®. The 20 KD-EGcellulase from Melanocarpus, which is obtainable from AB Enzymes,Finland, under the trade names Ecostone® and Biotouch® may also be used.Further commercial products from AB Enzymes are Econase® and Ecopulp®Another suitable cellulase from Bacillus sp. CBS 670.93 is obtainablefrom: Genencor under the trade name Puradax®. Further commercialproducts from Genencor are “Genencor detergent cellulase L” and IndiAge®Neutra.

Agents according to the invention may contain further enzymes which fallwithin the class of hemicellulases. These include, for example,mannanases, xanthan lyases, pectinlyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases andβ-glucanases. Suitable mannanases are obtainable, for example, under thename Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec®B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., SanDiego, Calif., USA. The β-glucanase isolated from B. subtilis isobtainable under the name Cereflo® from Novozymes.

In order to increase their bleaching action, detergents or cleaningagents according to the invention may contain oxidoreductases, forexample oxidases, oxygenases₁ catalases, peroxidases, such as halo-,chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenasesor laccases (phenol oxidases, polyphenol oxidases). Suitable commercialproducts which may be mentioned are Denilite® 1 and 2 from Novozymes.Compounds, preferably organic compounds, particularly preferablyaromatic compounds which interact with the enzymes, are advantageouslyalso added in order to enhance the activity of the oxidoreductases inquestion (enhancers) or, in the event of a major difference in redoxpotential between the oxidizing enzymes and the soiling, to ensureelectron flow (mediators).

The enzymes used in agents according to the invention either originallyoriginate from microorganisms, for instance of the genera Bacillus,Streptomyces, Humicola, or Pseudomonas, and/or are produced by suitablemicroorganisms using per se known biotechnological methods, for instanceby transgenic expression hosts from the genera Bacillus or filamentousfungi.

The enzymes in question are favorably purified by per se establishedmethods, for example by precipitation, sedimentation, concentration,filtration of the liquid phases, microfiltration, ultrafiltration,chemical action, deodorization or suitable combinations of these steps.

The enzymes may be added to the agents according to the invention in anyform established in the prior art. This includes, for example, solidpreparations obtained by granulation, extrusion or freeze-drying or, inparticular in the case of agents in liquid or gel form, solutions of theenzymes, advantageously as concentrated as possible, with a low watercontent and/or combined with stabilizers.

Alternatively, both for the solid and the liquid presentation, theenzymes may be encapsulated, for example by spray drying or extrudingthe enzyme solution together with a preferably natural polymer or in theform of capsules, for example those in which the enzymes are enclosed asa solidified gel or in those of the core-shell type, in which anenzyme-containing core is coated with a protective layer which isimpermeable to water, air and/or chemicals. Further active ingredients,for example stabilizers, emulsifiers, pigments, bleaching agents or dyesmay additionally be applied in superimposed layers. Such capsules areapplied in accordance with per se known methods, for example by agitatedor rolling granulation or in fluidized bed processes. Advantageously,such granules are low-dusting, for example due to the application of apolymeric film former, and stable in storage thanks to the coating.

It is furthermore possible to formulate two or more enzymes togethersuch that a single granular product displays two or more enzymeactivities.

A protein and/or enzyme present in an agent according to the inventionmay be protected, particularly during storage, from damage such as forexample inactivation, denaturation or degradation for instance due tophysical influences, oxidation or proteolytic cleavage. If the proteinsand/or enzymes are isolated from microbes, inhibition of proteolysis isparticularly preferred, in particular if the agents also containproteases. Agents according to the invention may contain stabilizers forthis purpose; the provision of such agents constitutes a preferredembodiment of the present invention.

One group of stabilizers comprises reversible protease inhibitors.Benzamidine hydrochloride, borax, boric acids, boronic acids or thesalts or esters thereof are frequently used, in particular derivativeswith aromatic groups, for instance ortho-, meta- or para-substitutedphenylboronic acids or the salts or esters thereof. Peptide aldehydes,in other words oligopeptides with a reduced C terminus, are alsosuitable. Peptide protease inhibitors which may inter alia be mentionedare ovomucoid and leupeptin; an additional option is the formation offusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are aminoalcohols such as mono-, di-,triethanol- and -propanolamine and mixtures thereof, aliphaticcarboxylic acids up to C₁₂, such as succinic acid, other dicarboxylicacids or salts of the stated acids. End group-terminated fatty acidamide alkoxylates may also be used as stabilizers.

Lower aliphatic alcohols, but especially polyols, such as for exampleglycerol, ethylene glycol, propylene glycol or sorbitol are furtherfrequently used enzyme stabilizers. Diglycerol phosphate also providesprotection from denaturation by physical influences. Calcium salts, suchas for example calcium acetate or calcium formate, and magnesium saltsare likewise used.

Polyamide oligomers or polymeric compounds such as lignin, water-solublevinyl copolymers or such as cellulose ethers, acrylic polymers and/orpolyamides stabilize the enzyme preparation inter alia with regard tophysical influences or fluctuations in pH. Polymers containing polyamineN-oxide act simultaneously as enzyme stabilizers and as dye transferinhibitors. Linear C₈-C₁₈ polyoxyalkylenes are other polymericstabilizers. Alkyl polyglycosides are likewise capable of stabilizingthe enzymatic components of the agents according to the invention andeven of enhancing their performance. Crosslinked nitrogenous compoundsperform a twin function as soil-release agents and as enzymestabilizers.

Reducing agents and antioxidants such as sodium sulfite or reducingsugars increase the resistance of the enzymes to oxidative degradation.

Combinations of stabilizers are preferably used, for example preparedfrom polyols, boric acid and/or borax, the combination of boric acid orborate, reducing salts and succinic acid or other dicarboxylic acids orthe combination of boric acid or borate with polyols or polyaminocompounds and with reducing salts. The action of peptidelaldehydestabilizers may be enhanced by combination with boric acid and/or boricacid derivatives and polyols and accordingly further strengthened by theadditional use of divalent cations, such as for example calcium ions.

The use of liquid enzyme formulations is particularly preferred for thepurposes of the present invention. Preferred agents according to theinvention are those which additionally contain enzymes and/or enzymepreparations, preferably solid and/or liquid protease preparationsand/or amylase preparations, in quantities of 1 to 5 Wt. %, preferablyof 1.5 to 4.5 and in particular of 2 to 4 wt. %, in each case relativeto the entire agent.

A wide range of the most varied salts may be used as electrolytes fromthe group of inorganic salts. Preferred cations are alkali metals andalkaline earth metals, preferred anions are halides and sulfates. From amanufacturing standpoint, it is preferred to use NaCl or MgCl₂ in thegranules according to the invention.

The exemplary embodiments presented in the following Figures illustratethe invention in greater detail. In the Figures

FIG. 1: shows a perspective view of a container with a blister packarranged by the container opening

FIG. 2 a: shows a blister pack for arrangement by a container openingand comprising a plurality of small portions

FIG. 2 b: shows a blister pack for arrangement by a container openingand comprising larger portions

FIG. 2 c: shows a blister pack for arrangement by a container openingand comprising portions separable into segments

FIG. 2 d: shows a blister pack for arrangement by a container openingand having bending lines

FIG. 2 e: shows a blister pack for arrangement by a container opening inthe bent state

FIG. 3 a: shows a blister pack in cross-section

FIG. 3 b: shows a blister pack in cross-section with a permeablemembrane and a sealing membrane

FIG. 4 a: shows a blister pack with snap-in closure

FIG. 5 a: shows a plan view of a dimensionally stable receiving meansfor additive portions

FIG. 5 b: shows a cross-section of a dimensionally stable receivingmeans for additive portions

FIG. 1 shows a particular embodiment of the invention, in which ablister pack (3), placed over the closure and pouring cylinder of thecontainer (1), is fastened to the container (1). A closure (2)comprising a peripheral shoulder (2 a) is arranged on the closure andpouring cylinder.

FIGS. 2 a-e show a detail view of an embodiment of the blister packaccording to the invention.

The blister pack (3) comprises an opening (4) which may be placed overthe pouring cylinder (2) of the container (1). In a further embodiment(not shown), it is also possible for the blister pack (3) to be placedfixably with the opening (4) over the closure (2) of the container (1).

The opening (4) of the blister pack (3) may be entirely or onlypartially closed, the opening (4) being designed such that it preventsat least simple detachment of the blister pack from the container.

One or more blister elements (5 a, 5 b) extend from the collar (7), eachelement comprising a plurality of cavities (6) which are conventionallyarranged over the surface (5 a, 5 b) of the blister pack (3).

The collar (7) is designed such that the closure (2), when in its closedposition, exerts a clamping force acting substantially perpendicularlyto the blister plane on the collar (7). The opening (4) of the blisterpack is here smaller than the shoulder (2 a) of the closure (2), suchthat, when the container is closed, the blister pack does not becomedetached from the container (1), but is instead held on the container(1) by the shoulder (2 a) of the closure (2). The shoulder (2 a) of theclosure (2) should be selected such that it may act at least in part onthe surface surrounding the opening (4) of the blister pack (1).

In one particularly preferred embodiment, the blister pack (1) has acircular opening (4) and two flat elements (5 a, 5 b) arranged radiallyrelative to the opening. The blister pack (3) is designed such that thetwo limbs (5 a, 5 b) of the blister pack (3) may in each case be liftedat their distal ends.

The blister pack (1) may, for example, be fastened to the container byan adhesive bond. The adhesive bond here extends only over a subarea ofthe blister pack (1) such that the remaining area may be lifted from thecontainer in order to press a product portion out of the blister pack(1)

FIG. 2 b shows a further particularly preferred embodiment of theinvention, in which the cavities (6) of the blister pack (3) extendsubstantially over the entire area of the blister elements (5 a, 5 b)arranged over the collar (7). These cavities (6) are in particularsuitable for accommodating larger product portions, as is for examplenecessary for long-lasting fragrancing of the surroundings of theblister pack (3).

FIG. 2 c shows a further embodiment of a blister pack (3) for fasteningto an outlet cylinder of a container (1). The blister pack (3) hascavities (6), which, thanks to the perforations (8) surrounding thecavities (6), are designed to be individually separable from the blisterpack (3).

Instead of perforations (8), it is also possible to provide other meansconsidered suitable by a person skilled in the art for separating aportion from the blister pack (3).

It is also possible to provide the perforations (8) only on thefilm/foil which seals the cavities (6), such that segment-by-segmentopening of the blister pack (3) is possible by peeling off thecorresponding portion of film/foil.

FIG. 2 d shows a blister pack (3) having an opening (4) which iscompletely or partially surrounded by a collar (7). A web (13) isarranged on the collar (7), said web having at least one predeterminedbending line (8).

According to a particularly preferred embodiment of the invention, theweb (13) comprises two predetermined bending lines (9) spaced apart fromone another. The distance (b) between the two predetermined bendinglines (9) spaced apart from one another should be selected such that itsubstantially corresponds to the height of the pouring cylinder (14).

The predetermined bending line (8) is conventionally a substantiallylinear weakening in the material of the web (13), which may for examplebe formed by perforation, provision of recesses or compaction of thematerial.

A blister element is arranged at the end of the collar (7) remote fromthe web (13), which element comprises a cavity (11) filled with aproduct and completely surrounded by a rim (10).

FIG. 2 e shows the blister pack according to FIG. 2 d placed over theclosure cylinder (14) of a container (1). The blister pack (3) is bentalong its predetermined bending lines (9) in each case by 90° in such amanner that the filled cavity (11) is positioned directly over theopening of the closure cylinder.

The cavity (11) of the blister pack (3) is designed such that it may besubstantially completely introduced into the opening of the closurecylinder (14).

According to a particularly preferred embodiment, the upper side of therim (10) in the bent state of the blister pack lies directly on the wallof the closure cylinder (14).

In a further particularly preferred embodiment, the rim (10)additionally comprises means which interact with the closure cylinder insuch a manner that the blister pack (3) is secured against lateralslippage on the closure cylinder. This may be achieved, for example, byan appropriately shaped circumferential groove or lug on the rim (10) ofthe blister pack (3).

In another embodiment of the invention, it is also possible, byappropriate selection of the spacing (b) of the predetermined bendinglines (9) and bending of the web (13) along the predetermined bendinglines (9), for the cavity (11) to be positionable in an appropriatelyshaped opening or surface of the closure (2) arranged on the closurecylinder (14).

FIG. 3 a shows a cross-section through a representative cavity (6, 11)of a blister pack (3) according to the invention. In the simplestembodiment, the cavity (6) filled with product (16) is formed by a lowerfilm/foil (17) and closed by a sealing film/foil (15). The material ofthe sealing film/foil (15) should be selected such that specificsubstances in the product (16), in particular fragrances, are notreleased to the surroundings.

The lower film/foil (17) consists of a material which is sufficientlystrong to avoid unintentional opening, but which can be opened by theapplication of appropriate pressure, for example by pressing with thethumb or tearing the film/foil with a fingernail. Exerting pressure on acavity (6) of the blister pack (3) results in pressure being exerted onthe product (16) located in the cavity (6), the product then ultimatelypuncturing the sealing film/foil (15).

The sealing film/foil may also be at least partially opened towards thecavity by tearing, piercing, rubbing, peeling, by contact with water, byheat, in particular by the heat of human skin, or other suitablemeasures.

According to a further embodiment of the invention, the blister pack (3)may also be configured such that the film/foil (17) forming the cavity(6) is so much stronger that the film/foil (17) forming the cavity (6)is opened by the applied pressure and the sealing film/foil (15) closingthe cavity (6) remains undamaged.

FIG. 3 b shows a further developed embodiment of the blister pack (3)which, in addition to the sealing film/foil (15), comprises a permeablemembrane (18). The permeable membrane (18) is arranged between thefilm/foil (17) forming the cavity (6) and the sealing film/foil (15),the sealing film/foil (15) preferably being arranged by a detachableadhesive bond over the surface of the permeable membrane (18).

The material and the properties of the permeable membrane (18) should beselected such that at least one substance in the product (16) may bereleased from the cavity (6) through the permeable membrane (18) to thesurroundings. In the simplest case, the permeable membrane (18)comprises a mesh which is suitable for retaining appropriate solids inthe cavity.

In particular, the properties of the permeable membrane (18) should beselected such that fragrances can be released from a liquid, gel-form orsolid product out of a cavity (6) to the surroundings.

The permeable membrane (18) is preferably adhesively bonded with thefilm/foil (17) forming the cavity (6) such that the permeable membrane(18) closes the cavities (6). The adhesive forces between the permeablemembrane (18) and the film/foil (17) forming the cavity (6) arepreferably greater than the adhesive forces between the permeablemembrane (18) and the sealing film/foil (15), such that, when thesealing film/foil (15) is peeled off, the permeable membrane (18)remains bonded to the blister pack (3) and closes the cavities (6).

FIG. 4 a shows another embodiment of the invention, in which a snap-inconnector element (19) is arranged on the blister pack (3), whichconnector element may be interlockingly connected, preferablydetachably, with a corresponding receptacle (20) on the packaging unit(1, 2, 14). It goes without saying that the blister pack (3) may alsocomprise a plurality of snap-in connectors (19, 20).

In one particularly preferred embodiment of the invention, the blisterpack (3) may also be fastened by an appropriate snap-in connector to theclosure (2) of the container (1).

According to a particularly preferred embodiment of the invention, theblister pack is at least in part provided with an adhesive layer whichis covered with a detachable sealing film/foil, whereby the blister pack(3) or individual portions (6) of the blister pack (3) may be fastenedto surfaces.

The products (16) disposed in the cavities (6) comprise in particular,but not exclusively, one or more substances selected from the groupcomprising fragrances, substances with a cleaning action, dyes, foamingagents etc.

FIG. 5 a shows a plan view of a dimensionally stable receiving means (3)for additive portions (21). The receiving means (3) comprises aplurality of receiving openings (22) for additive portions (21). Areceiving opening (22) interacts with an additive portion (21) in such amanner that the additive portion (21) is detachably fastened in thereceiving opening (22). This may be achieved, for example, by aninterlocking, frictional or materially bonded connection between theadditive portion (21) and the receiving opening (22). Fastening shouldin each case be provided such that the additive portion (21) cannotunintentionally fall out of the receiving opening (22), for exampleduring transport or storage.

In a preferred embodiment of the invention, the additive portion (21) isfastened in a receiving opening (22) by a detachable press fit. In afurther preferred variant embodiment, the additive portion (21) andreceiving opening (22) are fastened together by a detachable snap-inconnector.

The receiving openings (22) may for example take the form of athrough-hole or a blind hole. Any other design of the opening deemedobviously equivalent by a person skilled in the art is feasible, such asfor example openings with a rectangular, triangular or ovalcross-section.

The additive portion (21) comprises a closure which impermeably closesthe additive portion (21) relative to the surroundings. The closure isadvantageously designed such that the additive portion (21) can beclosed in fluid-tight manner relative to the surroundings. The closureis particularly preferably designed such that the additive portion (21)may be closed substantially impermeably with regard to the emission offragrances.

The closure is arranged detachably on the additive portion (21) ininterlocking, frictional or materially bonded manner. In particular, theadditive portion (21) may be impermeably closable relative to thesurroundings by the closure by means of a press fit, a screw closure, asnap-in connector or adhesive bonding.

In a further embodiment, the additive portion (21) is closed with abung. The bung preferably consists of a resilient material and isdesigned such that it closes the additive portion (21) in at leastfluid-tight manner.

It is furthermore conceivable to provide the additive portion (21) withsealed openings. The openings may take the form of holes through thelateral, bottom or top surface of the additive portion (21). Any othersuitable form for the openings is, however, also feasible, such as forinstance slots, meshes etc. The seal of the openings is designed suchthat the openings are closed in fluid-tight manner. In one particularlypreferred embodiment, the seal is substantially impermeable with regardto the emission of fragrances from the portion volume into thesurroundings. The seal may in particular comprise a plastics film whichis at least in part, preferably detachably, adhesively bonded with thesurface of the additive portion. It is also conceivable to seal theopenings by means of a “sleeve”, a suitable plastics film being drawntautly around the portion container.

In another embodiment, the additive portion (21) is filled with anon-free-flowing substance. In this case, the additive portion may beshaped like a cup which has an open end face. Alternatively, theadditive portion (21) could also comprise openings on its lateralsurface.

In this connection, non-free-flowing means that the substance disposedin an additive portion cannot escape into the surroundings through theopenings. This may be achieved, for example, by using a solid or solidgranules, the size of the solid granules being set, for example, suchthat they do not fit through the openings or the solid is fastened inthe portion volume.

The additive portions may be arranged in two positions in the receivingmeans (3). In a first, closed position, the openings of the additiveportion (21) are completely closed by the lateral or bottom surface ofthe receiving opening (22).

As is apparent from FIG. 5 b, it is possible, by taking an additiveportion (21) out of the receiving opening (22), to arrange the additiveportion (21) in a second position in a receiving opening (3) of thereceiving means (3), in which the openings of the additive portion (21)correspond with the surroundings and constituents of the substancelocated in the additive portion (21) are released, preferably bydiffusion, into the surroundings.

Additionally, in this case, the opening or openings of the additiveportion (21) may be covered by a protective film which initiallyprevents release of the product into the surroundings by diffusion. Theprotective film may be removed for example by tearing or rubbing, suchthat product may then be released into the surroundings.

The receiving means (3) comprises an opening (4) which is detachablyconnected to the opening of the container in interlocking, frictional ormaterially bonded manner. In a preferred embodiment of the invention,the receiving means (3) comprises an opening (4) which may be placedover the pouring cylinder of the container. The opening (4) may here beentirely or only partially closed, the opening (4) being designed suchthat it prevents at least simple detachment of the receiving means fromthe container. Alternatively, it is also possible to connect thereceiving means (3) detachably to the container closure in interlocking,frictional or materially bonded manner.

1-15. (canceled)
 16. A packaging unit, comprising: a container (1) foraccommodating a product, said container having an opening (14) fordischarging the product from the container, a closure (2) for coveringthe opening (14), and at least one receiving means (3) having at leastone additive portion (6, 11, 21) for holding an additive prior todispensing such additive into the product, wherein the receiving means(3) is detachably fastenable to the container (1) or the closure (2) orboth.
 17. The packaging unit as claimed in claim 16, wherein thereceiving means (3) comprises a first means (4, 7, 19) for fastening thereceiving means (3) to the container (1) or closure (2) or both, whichfirst means interacts in such a manner with a second means (2, 14, 20)arranged on the packaging unit (1, 2, 14) so that the receiving means(3) is detachably fastenable, substantially in interlocking, frictionalor materially bonded manner, to the container (1) or closure (2) orboth.
 18. The packaging unit as claimed in claim 17, wherein thereceiving means (3) has an opening (4) that may be placed over a closurecylinder (14) of the container (1) so that the receiving means (3) isheld in contact with the container (1) by the closure (2).
 19. Thepackaging unit as claimed in claim 17, wherein the first and secondmeans for fastening the receiving means (3) to the packaging unit form asnap-in connector.
 20. The packaging unit as claimed in claim 16,wherein the additive portions take the form of a blister pack.
 21. Thepackaging unit as claimed in claim 20, wherein the receiving means (3)defines a cavity (11) and includes a web (13), and wherein said web (13)comprises at least two predetermined bending lines (9), along which thereceiving means (3) may be bent in such a manner that the cavity (11)may be positioned substantially in an opening defined by a closurecylinder (14) of the container (1).
 22. The packaging unit as claimed inclaim 20, wherein at least some of the additive portions (6) aresurrounded by at least one perforation line (8) in such a manner that anindividual additive portion or group of additive portions (6) isseparable from the blister pack (3) along one or more perforation lines(8).
 23. The packaging unit as claimed in claim 20, wherein the additiveportion (6) is formed with a film/foil (17) and a removable sealingfilm/foil (15), and on removal of the sealing film/foil (15), apermeable membrane (18) adheres to the receiving means (3) and closesthe additive portion (6).
 24. The packaging unit as claimed in claim 20,wherein the receiving means (3) comprises an adhesive portion with anadhesive layer which is covered with a detachable sealing film/foil. 25.The packaging unit as claimed in claim 16, wherein the receiving means(3) is substantially dimensionally stable and comprises receivingopenings (22) which are designed such that additive portions (21) aredetachably fastenable in the receiving openings (22) in interlocking,frictional or materially bonded manner.
 26. The packaging unit asclaimed in claim 25, wherein the additive portions (21) comprise atleast one opening which is closable with a closure means.
 27. Thepackaging unit as claimed in claim 25, wherein the additive portions(21) comprise at least one opening which interacts with the receivingopenings (22) in such a manner that the opening of an additive portion(21) fastened in the receiving opening (22) is closed.
 28. The packagingunit as claimed in claim 25, wherein the at least one additive portion(21) contains a non-free-flowing substance (16).
 29. The packaging unitas claimed in claim 16, wherein a first additive is held within at leastone additive portion (6, 21) and a second additive that differs withregard to its fragrance, surfactant, and/or dye composition from thefirst additive is held within at least one other additive portion (6,21).
 30. The packaging unit as claimed in claim 16, wherein at least onepart of the receiving means (3) is adhesively bonded to the container(1), or the closure (2) or both.
 31. A holder for flowable productadditives to be dispensed into a product, comprising: a receiving means(3) having at least one receiving opening (22) for receiving an additiveportion (21) that holds one or more additives prior to dispensing suchadditive(s) into the product, wherein the receiving means (3) issubstantially dimensionally stable and is detachably fastenable to aproduct container, or a closure releaseably connectable to the productcontainer (2), or both, and wherein the additive portions (21) aredetachably fastenable in the receiving openings (22) in interlocking,frictional or materially bonded manner.
 32. The holder as claimed inclaim 31, wherein the receiving means (3) has a plurality of receivingopenings (22) and associated additive portions (21), and the additiveportions (21) comprise at least one opening which interacts with thereceiving openings (22) in such a manner that the opening of oneadditive portion (21) fastened in its associated receiving opening (22)is closed.
 33. The holder as claimed in claim 31, wherein the receivingmeans (3) has a plurality of receiving openings (22) and associatedadditive portions (21), and wherein a first additive is held within atleast one additive portion (21) and a second additive that differs withregard to its fragrance, surfactant, and/or dye composition from thefirst additive is held within at least one other additive portion (21).